KR20190016116A - Method for increasing the volume capacity in a gas storage and discharge system - Google Patents

Abstract

The present invention provides a gas storage system comprising a porous gas sorbent monolith, porous gas sorbent monolith of the present disclosure having excellent work capacity and volume capacity, a method of manufacturing the same, and a method of storing gas. The porous gas adsorbent monolith includes a gas adsorbing material and a non-aqueous binder.

Description

Method for increasing the volume capacity in a gas storage and discharge system

This application claims priority to U.S. Provisional Application No. 62 / 357,613, filed July 1, 2016, and U.S. Provisional Application No. 62 / 464,955, filed February 28, 2017, The contents of which are incorporated herein by reference.

This disclosure relates to gas storage systems, and more particularly to porous gas adsorptive monoliths and storage systems for adsorbent gases having improved storage and delivery capacity. In addition, the present description can be applied to adsorbed gas storage systems (e. G., Activated carbon containing storage systems or adsorptive monolith-containing storage systems, including adsorbed < RTI ID = 0.0 & And a method for improving the working capacity or reversible storage of natural gas storage and delivery from natural gas storage systems.

An adsorbed natural gas (ANG) storage system is an alternative to the current use of compressed natural gas (CNG) cylinders due to lower operating pressures. Reduction of the operating pressure enables the use of a home refueling unit, reduces compression costs, and is inherently safer. Typically, the ANG storage system has an operating pressure of less than 1,000 psig as compared to a CNG cylinder having an operating pressure in the range of 3,000 to 3,600 psig.

In the ANG storage system, the adsorbent is used to store natural gas molecules, which fill a specific molecular-sized porosity with a " condensed phase " attached to the surface and adsorbed. The adsorbent is placed in a gas cylinder, or a gas cylinder is formed around the adsorbent, and the adsorbent is then purged to remove oxygen. The adsorbent should exhibit a high volumetric working capacity and the ratio of the gas released from the adsorbent to the gas stored in the adsorbent should ideally be one. The use of an adsorbent in the ANG storage system allows the gas cylinder to retain a larger mass of natural gas relative to the empty cylinder at comparable pressures. These adsorbents include activated carbon from various sources including wood, peat, coal, coconut, synthetic or natural polymers, and various processes including chemical and / or thermal activation. Furthermore, inorganic adsorbents including molecular sieves, porous alumina, columnar clays, porous silica, zeolites and metal organic frameworks can be used.

Adsorption of gas molecules on the surface of the solid and formation of the condensation phase in the pores is a phenomenon of exotherm. In ANG applications, primary adsorption is known as van der Waals force or weak force interactions. In the case of adsorbing gas molecules, heat is released because the molecules have reduced degrees of freedom (vibrational, rotational, or translational). When a large amount of gas is adsorbed, the amount of heat released may be significant. In contrast, desorption of gas molecules is an endothermic process, which means that energy (i.e., heat) is adsorbed by the gas molecules. Again, when a significant amount of gas is released, a significant temperature reduction is recorded in the system.

The most abundant component of natural gas, methane, has a kinetic diameter of 3.8 Å. The computer simulation suggests that the ideal pore size (e.g., diameter) of the adsorbent to store methane is about 9-12 ANGSTROM. Historically, the focus of research on adsorbents for methane storage has focused not only on maximizing the pore volume in this size range, but also on achieving a narrow pore size distribution around a pore size range of about 9-12 Å. See, for example, US 5,965,483; US 5,416,056; US 5,372,619; US 5,614,460; US 5,710,092; US 5,837,741; US 6,626,981; US 5,626,637; US 8,691,177; US 8,158,556; US 8,500,889; US 8,915,989; US 5,401,472; US 9,102,691; US 7,060,653; US 5,998,647; US 7,662,746; US 8,231,712; US 2014/0018238; And WO 2014/0274659.

One limitation of the effort towards pore size distribution in the range of about 9-12 ANGSTROM is that it maximizes storage while this pore size range is not correlated with the delivered gas when depressurized to ambient pressure. The adsorbent performance from an actual point of view should exceed the total amount of gas stored at the total gas capacity, the maximum operating pressure and should focus on the total amount of gas released when drawn at ambient pressure, ie 14.7 psi do. A narrow pore size distribution of about 9-12 A pore size inherently has more gas molecules when depressurized from high pressure to ambient pressure due to the effect of the carbon surface surrounding the gaseous molecules. In addition, natural gas compositions are well known for containing larger sized molecules such as ethane, butane and propane. A typical composition of natural gas is in the range of 89-95% methane. A surprising aspect of the present disclosure is the surprising and unexpected finding that the distribution of voids in the storage area and larger voids (up to 25-30 A) facilitates release and release during reduced pressure, to be. It was also surprisingly and unexpectedly advantageous to minimize the pore volume of < 9 A in order to better maintain the initial capacity over many refueling cycles. It was also unexpected that pore volumes greater than 27 ANGSTROM, and even greater than 50 ANGSTROM, would further enhance storage capacity. Furthermore, many past attempts to centralize the pore size distribution of adsorbents in the 9-12 angstroms have resulted in very complex activation methods and / or extraneous substances due to the very narrow pore size distribution. The use of this manufacturing method has not yet been proven to be very costly and / or capable of increasing scale either economically or economically. In some cases, improved volumetric capacity or volumetric performance of the adsorbent material (L of adsorbent per GGE, where GGE is the gasoline defined as 5.66 lbs of natural gas according to US Department of Energy Alternative Fuels Data Center) Gasoline gallon equivalent (www.afdc.energy.gov/fuels/equivalency_methodology.html), but gravimetric working capacity or gravimetric performance (lb of adsorbent per GGE) Sacrifice. In other cases, an inverse was observed, that is, the weight work capacity was increased at the expense of the reduced volume capacity.

More recent research has focused on determining how to reduce the amount of gas stored or retained in adsorbent material at ambient pressure, in addition to improving adsorbent capacity. One way to do this is to control the temperature of the system. Once the temperature is controlled, heat can be applied to facilitate the release of gas molecules when the tank is depressurized, i. E. When supplying fuel to the engine. Conversely, heat can be removed when the tank is pressurized, i.e., during refueling of the ANG tank, to further increase the amount of stored gas at the specified operating pressure. In certain cases, the use of an external energy source has been proposed which is applied to tanks, adsorbents or other additives including heat transfer properties applied to tanks or adsorbents. See, for example, US 5,912, 424; US 7,955,415; US 7,418,782; US 7,891,386; US 7,735,528; US 7,938,149; US 9,006,137; US 9,188,284; CN 2006/10013838; WO 2015/02262; US 2014/0290283; And US 2014/0290611. These methods improve the emission of gas molecules or allow adsorption close to isothermal conditions, but they add weight and cost as well as complicate the overall system. That is, it has not yet been proven that these methods are commercially viable due to the mentioned disadvantages.

Compared to the workload focused on the pore size distribution, the property of the relatively neglected adsorbent is the structure of the adsorbent. Most adsorbents on the market today can be confined to three categories: powder, pellets and granules. The size of the category is typically 0.025 to 7 mm. These materials are introduced into their packages by loading them from overhead, resulting in a random packing density so that the adsorbent occupies at most about 64% of the inner volume of the container. In some cases, a vibrating device can be used in the container to slightly increase the occupied volume by 65-70%. However, about one-third of the container remains without adsorbent. In order to maximize the internal volume of the cylinder, a more conforming structure, which reflects the internal shape, is required, which also makes filling easier and faster, as compared to particulate filling which requires vibration treatment. In some cases, carbon particles or carbon fibers are attached together using an organic binder to increase the bulk density or to use carbonizable binders. See, for example, US 5,614,460; US 5,837,741; US 6,030,698; US 6,207,264; US 6,475,411; US 6,626,981; US 2014/0120339; US 2015/0258487; US 2009/0229555 and US 8,691,177 B2. On the other hand, lighter weight systems for natural gas storage will have added value. For example, U.S. Pat. The Department of Energy's Office of Energy Efficiency and Renewable Energy's Vehicle Technologies Office (https://energy.gov/eere/vehicles/vehicle-technologies-office-lightweight-materials-cars-andtrucks) -8% fuel economy improvement, which corresponds to a reduction of about 1% for a 30 Ib weight reduction for a 2000 Ib vehicle, so we prefer a smaller binder and lighter weight adsorbent for fuel storage. Thus, a preferred, but difficult, goal is to provide a lightweight, lightweight, lightweight, lightweight, lightweight, lightweight, lightweight, lightweight, Shaped, compliant, structured article.

One limitation to many structured articles is that the working capacity decreases when the adsorbent is mixed with the binder material. Depending on the binder material, the degree of performance reduction exceeds the simple dilution of the adsorbent. The reduction in natural gas adsorption and desorption performance is believed to be due to the reduction of the total pore diameter causing the occluding of the pores, limited molecular diffusion and effusion in the relevant pore size range, and the obstruction of the adsorbent surface. Currently used binders, such as, but not limited to, water soluble binders (e.g., polar binders), including but not limited to carboxymethyl cellulose (CMC), methyl cellulose, crystalline salts of aromatic sulfonates, polyfurfuryl alcohol, . The aqueous solvent produces a gel emulsion that solubilizes the binder and acts to attach the carbon particles together. Resulting in degraded performance of the neat adsorbent, which is inherent to the process, porous and surface-clogged. Alternatives to aqueous binders include certain non-solubilized, non-solubilized binders such as clays, phenolic resins, polyacrylates, polyvinyl acetate, polyvinylidene chloride (PVDC), ultra high molecular weight polyethylene (UHMWPE) , non-aqueous binders. However, it has been observed that the binder group reduces the overall porosity of the adsorbent due to pore blocking or pore filling. The two groups of binders include binders that are typically carbonized or annealed at high temperatures (> 700 ° C), which causes void shrinkage and pore volume loss. The cumulative effect yields an adsorbed article characterized by a distorted pore size distribution and degraded pore volume relative to the component adsorbent material. Furthermore, in certain cases, the limitations have been in the manufacture of the article. In these particular cases, shape-specific articles are used in combination with the cost of scale-up to mass production, where the decomposition from corrosive gas by-products (e.g., carbonization of polyvinyl chloride-type polymers) Products), and they either stop their adaptation or narrow their use to a niche market.

Furthermore, the process that causes void shrinkage results in distorted dimensions of the final molded article. The ideal part can be formed into the internal shape of the cylinder to maximize the volume capacity of the tank. This is considered to be important to the application. When the adsorbent is bound by, for example, CMC (aqueous) or PVDC (non-aqueous), the final dimensions of the dried and / or carbonated features are reduced and / or distorted relative to the initial dimensions. This disadvantage, called shrinkage, is difficult to control because it can not control the chemical chemistry at the molecular level at the interface of the adsorbent and the binder. The concluding effect is that there is considerable additional void space between the outer wall and the inner cylinder wall to accommodate variable shrinkage when the molded part is installed in the cylinder. Exceeding the reduced volume capacity, the vacant space-bound adsorbent moves within the cylinder, which can lead to entrained particles in the potentially depressurized gas, reducing the adsorbent in the tank and potentially clogging the downstream line have. The storage capacity can be remarkably reduced due to the cumulative effect. One way to prevent shrinkage is to employ large-sized targets on the initial part. However, since shrinkage is difficult to predict, some components may inevitably have a final external dimension that is too large to fit within the range of fuel tanks produced.

Accordingly, it is an object of the present invention to provide a porous, non-aqueous binder having the non-aqueous binder described herein that does not reduce the storage capacity of the gas, overcomes the process challenges of conventional binders, and has more reliable final physical dimensions and adsorptive performance There is a need for a gas-absorbing article, a lightweight and improved adsorbent density, a high workload capacity, and a level of capacity maintained by repeated lubrication, and a method of making the same.

The present disclosure relates to a method for manufacturing a porous gas adsorbent monolith (e.g., activated carbon monolith), a porous gas adsorbent monolith, and a method and system for utilizing the same. In particular, surprisingly and unexpectedly, it has been found that certain combinations of gas adsorbing material and non-aqueous binder characterized by a significant pore volume of about 9-27A, as described herein, provide better and more predictable dimensions, volume capacity and / Or weight capacity of the porous gas adsorbent monolith.

In certain embodiments, about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or more (including all values and ranges between) Lt; / RTI &gt; In certain embodiments, voids in excess of 50%, 60%, 70%, 80%, 90%, 95% or more (including all values and ranges between) are in the range of 9-27A. In certain embodiments, voids in excess of 60% are in the range of 9-27A. In certain embodiments, voids in excess of 70% are in the range of 9-27A. In certain embodiments, voids in excess of 80% are in the range of 9-27A. In certain embodiments, voids in excess of 90% are in the range of 9-27A. In certain embodiments, voids in excess of 95% are in the range of 9-27A. In certain other embodiments, about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% And is in the range of about 12-27 ANGSTROM. In certain embodiments, pores (including all values and ranges between) in excess of 50%, 60%, 70%, 80%, 90%, 95% or more are in the range of about 12-27A. In certain embodiments, voids in excess of 30% are in the range of 12-27A. In certain embodiments, voids in excess of 40% are in the range of about 12-27 ANGSTROM. In certain embodiments, pores greater than 50% are in the range of about 12-27 ANGSTROM. In certain embodiments, pores greater than 60% are in the range of about 12-27A. In certain embodiments, voids in excess of 70% are in the range of about 12-27A. In certain embodiments, voids in excess of 80% are in the range of about 12-27A.

For example, in any aspect or embodiment described herein, the monolith has: a volume of about 100 cc / L-M at a pore size of less than about 9 angstroms; &Gt; about 200 cc / L-M volume at about 9-27 A pore size; &Gt; about 50 cc / L-M volume in pores of about 27-490 ANGSTROM; Or a combination thereof.

One aspect of the present disclosure provides a microporous or nanoporous, monolithic carbonaceous article. The article includes a gas adsorbing material and a " non-aqueous " binder as described herein. By " non-aqueous " is meant a binder which is primarily dense by mechanical bonding mechanisms and which binds and binds the powder adsorbent in the adsorbent monolith structure. The binder is added as an emulsion, as a dispersion in a solvent or as a dry powder, and the binder is not in the form of a gel, or may not be solubilized by a solvent, which may or may not be water. In certain embodiments, the non-aqueous binder of the present disclosure may include a fluoropolymer (e.g., poly (vinylidene difluoride)), polytetrafluoroethylene, fluorinated ethylene propylene or perfluoroalkoxyalkane, (E.g., nylon-6,6 'or nylon-6), polyamides, fibrillated cellulose, high-performance plastics (e.g., polyphenylene sulfide), copolymers with fluoropolymers , A copolymer with a polyamide, a copolymer with a polyimide, a copolymer with a high-performance plastic, or a combination thereof. The high performance plastic, high performance polymer or high performance thermoplastic resin may be any semi-crystalline or amorphous thermoplastic resin having a continuous service temperature of 150 ° C or higher. In certain embodiments, the non-aqueous binder of the composition of the present disclosure is present in an amount of 15 wt% or less. In one embodiment, the non-aqueous binder is polytetrafluoroethylene. In any aspect or embodiment described herein, the non-aqueous binder of the present disclosure is in the form of polytetrafluoroethylene. In other embodiments, the non-aqueous binders of the present disclosure may comprise up to 10 wt% (e.g., less than 10 wt%, 7 wt%, about 2.5 wt% to 7 wt%, or about 3 wt% to about 7 wt% &Lt; / RTI &gt;

Without wishing to be bound by theory, a surprising advantage of the non-aqueous binders described herein is that it is possible, without mechanical coating of the mask or the outer surface of the adsorbent particle, to minimize contamination of the inner adsorbent particle porosity by the binder, It is considered to be a property of immobilizing and bonding the powder adsorbent to the outer surface. Mechanical adhesion refers to the fact that the non-aqueous binder described in this disclosure conforms somewhat to the irregularities of the surface of the adsorbent particles from the imposition of temperature and / or pressure, and thereafter is cured in some way, bonded, To form an immobilized adsorbent structure. Adhesion is achieved by contact with the adsorbent by means of particles of low aspect ratio shape and / or binder in the form of fibers of higher aspect ratio. Fiber binders may be added at higher aspect ratios or may be produced by processes. For example, at a temperature in the vicinity of the binder softening point, during the heating and compression molding or extrusion shaping steps of the blend during the shear mixing process step, the desired fiber- And can assist in the efficient use of the binder for the desired mechanical bonding. By suitably selecting the binder and drying the blend of binder and adsorbent before molding, undesirable shrinkage is prevented and the desired target dimension of the monolith can be achieved reliably and reproducibly.

Additional advantages of embodiments of the present disclosure, such as the use of adsorbents having significant porosity in the range of about 9-27 ANGSTROM in contrast to being concentrated in binder selectivity, relatively low binder content, and smaller, about 9-12 ANGSTROM porosity Is that the weight of the fuel storage tank is lower. That is, in certain embodiments, the monolith has a pore size of less than about 9 A < about 100 cc / L-M volume; &Gt; about 200 cc / L-M volume at about 9-27 A pore size; &Gt; about 50 cc / L-M volume in pores of about 27-490 ANGSTROM; Or a combination thereof.

In some embodiments, the gas adsorbing material is selected from the group consisting of activated carbon, zeolites, porous silica, covalent organic frameworks or metal organic frameworks. In certain embodiments, the gas adsorbent material is present in an amount of at least 85 wt% (e.g., at least 90 wt%, greater than 90 wt%, at least 93 wt%, or greater than 93 wt%).

In a further embodiment, the gas adsorbing material is particulate activated carbon. In certain embodiments, activated carbon is selected from the group consisting of, for example, a nut shell, a coconut shell, a peat, a wood, a coir, a lignite, a coal, a petroleum pitch, Lt; / RTI &gt; In certain embodiments, the activated carbon is in powder or granular form.

In certain embodiments, the activated carbon monolith has a pore volume of ≥ 0.5 cc / g for pores ranging in size from about 9 Å to about 27 Å (ie, diameter).

In another embodiment, the monolith has a part density of at least 0.4 g / cc. In one embodiment, the part density ranges from about 0.4 g / cc to 0.8 g / cc.

In certain embodiments, the monolith has a working weight capacity or weight performance of 40 lbs / GGE (e.g., &lt; = 30 lb / GGE). In certain embodiments, the working weight capacity is 28 lbs / GGE or less.

In a further embodiment, the monolith has a volume capacity of 35 L / GGE or less. For example, the volumetric capacity may be less than 30 L / GGE or less than 25 L / GGE.

Another aspect of the disclosure provides a method of making a porous gas sorbent monolith. The method comprising: mixing a gas adsorbing material and a non-aqueous binder as described herein; Compressing or extruding the mixture into a forming structure; And applying heat to the compacted or extruded mixture. In one embodiment, the method further comprises placing the mixture in a tank and then compressing the mixture.

Another aspect of the present disclosure provides a method of making a porous gas adsorbent monolith. The method comprising: mixing a gas adsorbing material and a non-aqueous binder as described herein; Compressing the mixture in a tank; And applying heat to the compressed mixture and / or the tank.

In some embodiments, the monolith has at least one of the following: a non-aqueous binder of the present disclosure is a fluoropolymer, a polyamide, a fibrillated cellulose, a polyimide, a high-performance plastic (e.g., , Polyphenylene sulfide), a copolymer with a fluoropolymer (e.g., poly (vinylidene difluoride) or polytetrafluoroethylene), nylon-6,6 ', nylon-6' A copolymer with a polyimide, a copolymer with a high-performance plastic; Or the gas adsorbing material is selected from the group consisting of activated carbon, zeolite, porous silica, covalent organic skeleton or metal organic skeleton.

In one embodiment, the monolith has at least one of the following: the gas adsorbing material is present in an amount of at least 90 wt% (e.g., at least 93 wt%); The non-aqueous binder is present in an amount of 10 wt% or less (e.g., 7.5 wt% or less, 7 wt% or less, about 2.5 wt% to about 7 wt%, or about 3 wt% to about 7 wt%); Or a combination thereof.

In a further embodiment, the monolith has at least one of the following: a part density of at least 0.4 g / cc (e.g. in the range of about 0.40 g / cc to about 0.8 g / cc, about 0.4 g / cc or about 0.65 g / cc, or about 0.4 g / cc to about 0.6 g / cc); A working weight capacity of less than 40 lbs / GGE (e.g., less than 30 lbs / GGE or less than 28 lbs / GGE); A volume capacity of less than 35 L / GGE (e.g., less than 30 L / GGE or less than 25 L / GGE); The gas adsorbent material is present in at least 93 wt%; The non-aqueous binder is present in an amount from about 2.5 wt% to about 7 wt%; The pore volume of a pore having a size ranging from about 9 A to about 27 A is ≥ 0.5 cc / g; Or a combination thereof.

In certain embodiments, compressing the mixture comprises applying a pressure of at least 1,250 psi. For example, the applied pressure may be greater than 1,500 psi.

In certain embodiments, the forming structure or extruded shape is substantially at least one of a cylinder, an oval prism, a cube, an elliptical prism, a right angled prism, or an irregular shape.

A further aspect of the present disclosure provides a gas storage system. The gas storage system may comprise an envelope or container (i.e., a tank or vessel) disposed therein and a porous gas adsorbent monolith of the present disclosure disposed therein (e.g., a gas adsorbent material as described herein and a non- - a monolith containing an aqueous binder). In certain embodiments, the envelope or container defines a body having an internal dimension and an internal volume. In certain embodiments, the adsorbent comprises about 80% to about 99% of the inner volume of the envelope or container. In certain embodiments, the container is a canister.

In one embodiment, the container is configured to withstand at least 1,000 psi.

In some embodiments, the monolith has at least one of the following: a non-aqueous binder of the present disclosure is a fluoropolymer, a polyamide, a polyimide, a fibrillated cellulose, a high-performance plastic At least one binder selected from the group consisting of a copolymer with a fluoropolymer, a copolymer with a polyamide, a copolymer with a polyimide, or a combination thereof; Or the gas adsorbent material is selected from the group consisting of activated carbon, zeolites, silica, covalent organic frameworks or metal organic frameworks.

In another embodiment, the monolith comprises a gas adsorbent material in an amount of at least 90 wt%; And a non-aqueous binder in an amount up to 10 wt%.

In a further embodiment, the monolith has at least one of the following: a part density of at least 0.4 g / cc; Working weight capacity less than 40 lbs / GGE; A volume capacity of less than 35 L / GGE, or a combination thereof.

The preceding general usage areas are provided by way of example only and are not intended to limit the scope of the present disclosure and the appended claims. Additional objects and advantages associated with the compositions, methods, and processes of the present disclosure will be recognized by those skilled in the art from the claims, detailed description, and examples herein. For example, various aspects and implementations of the present disclosure may be utilized in various combinations, all of which are expressly contemplated by the present disclosure. These additional advantages, objects, and implementations are expressly included within the scope of this disclosure. The specific examples for providing publications and other data used herein to identify the background of the disclosure and additional details of implementation are incorporated by reference in their entirety for all purposes.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate some embodiments of the disclosure and, together with the description, serve to explain the principles of the disclosure. The drawings are merely for the purpose of illustrating embodiments of the present disclosure and should not be construed as limiting the invention. Additional objects, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate an exemplary embodiment of the present disclosure.
1A shows an empty cylinder (i.e., tank or vessel) of a gas storage system;
1B shows a cylinder (i.e., tank or vessel) of a gas storage system in which a gas adsorbent pellet is contained;
1C shows a cylinder (i.e., a tank or vessel) of a gas storage system having a shape-specific gas adsorbent material;
2 is a flow diagram of a method of manufacturing a monolith of the present disclosure;
Figure 3 shows the gas storage system of the present disclosure;
4 is a graph depicting the sorbent of the present disclosure and the pore volume for each monolith, 9-27 A (cc / g) normalized to the weight percent of adsorbent;
5 is a graph showing the correlation between the pore volume of the monolith of this disclosure 9-27A and the reversible natural gas storage capacity (wt% when pressurized to 900 psig);
Figure 6 is a graph showing the correlation of pore volume 9-12 ANGSTROM with reversible natural gas storage capacity (wt% when pressurized to 900 psig);
Figure 7 shows the dimensional change encountered by the cylindrical puck monolith fabricated in the alternative binder formulation between the initial shape of the monolith (i.e., die inner diameter) and any subsequent subsequent heating and / &Lt; / RTI &gt;
Figure 8 shows the relationship between the initial shape of the monolith (i.e., the initial diameter of the die and the length of the initial compression or cut of the cylinder) and any subsequent subsequent heating and / or drying process steps to a cylindrical puck monolith Compare the volume changes encountered by them;
Figure 9 shows an exemplary pore volume and recoverable reversible storage capacity of an exemplary monolith according to the present disclosure on a monolith volume basis;
Figure 10 shows the degradation of the reversible natural gas capacity in repeated saturation and purge cycles by the less microporous (&lt; 9A in size) embodiment of this disclosure compared to the heavy microporous comparative example, Lt; / RTI &gt;
Figure 11 shows the continuous deterioration of the reversible natural gas capacity after 10 cycles of saturation and purge cycles by a comparative microporous comparative example compared to the stabilized reversible capacity according to the less microporous embodiment of this disclosure;
Figure 12 is a graph showing the correlation between the percent loss of the reversible natural gas capacity and the retentivity of the monolith against natural gas (on a volumetric monolith basis, for both the examples of this disclosure and the comparative examples, Capacity, less than reversible capacity);
Figure 13 shows the retention (saturation capacity, less than reversible capacity) of the monolith against natural gas for the first pressurization-depressurization cycle of the test for both the examples of this disclosure and the comparative examples on a volumetric monolith basis, A graph showing the correlation of the volume;
FIG. 14 is a graph showing mesopore volumes of 27-490 ANGSTROM versus pore volumes less than 9 ANGSTROM for both the examples and comparative examples of the present disclosure on a volumetric monolith basis;
15 is a graph comparing pore volumes of 9-12 ANGSTROM to less than 9 ANGSTROM sizes for both the Examples and Comparative Examples of the present disclosure on a volumetric monolith basis; And
16 is a graph comparing pore volumes of 9-27 ANGSTROM to less than 9 ANGSTROM sizes for both the examples and comparative examples of this disclosure on a volumetric monolith basis.

The following is a detailed description provided to assist one skilled in the art in practicing the present disclosure. Those of ordinary skill in the art will be able to modify and modify the embodiments described herein without departing from the spirit or scope of the disclosure. All publications, patent applications, patents, drawings and other references mentioned herein are expressly incorporated by reference in their entirety.

Currently described are gas sorbent monoliths and methods of making them, as well as gas storage systems using them, all of which require that the required pore size range of the adsorbent for storing and releasing natural gas be from about 9 A micropores to about 27 A And a surprising and unexpected discovery that it should be a distribution of mesopores in size. In FIG. 5, a strong correlation between pore volume of about 9 A to about 27 A size and reversible natural gas storage (@ 900 psig in weight) is mentioned. As shown in Fig. 6, the correlation is not clear when the pore volume of 9-12A is plotted against the reversible natural gas storage (@ 900 psig in weight%). Thus, prior natural gas storage operations have focused on methane, its adsorption and small micropores that may have an improved adsorption capacity for the gas, but a better design of the adsorbent for reversible natural gas storage, There is a need to consider larger size pores that extend into the range. Further, while typical binders seriously occlude this micropore size range, the use of the binders of this disclosure does not seriously occlude voids or porosity of the preferred size described above in the mesopore range. As shown in FIG. 4, the advantage of the non-aqueous binder of the present disclosure over the previously used aqueous binder is how close to the 9-27 A porosity of the resulting monolith article is the most preferred porosity of 9-27 A of the adsorbent component (I.e., y = x is closer to the Line of Equivalence) and is less variable. That is, compared to conventional binders, monoliths made with the binders described herein exhibit less loss of pore volume of 9-27 A preferred size of the component adsorbent and less variability of pore volume of 9-27 ANGSTROM, &Lt; / RTI &gt; Also, as illustrated below, the binder of the present disclosure is a high density monolith (i.e., a monolith with a maximum adsorbent content of the monolith) that is formed to be close to and securely installed within the interior dimensions of a natural gas fuel tank, / RTI &gt; This finding substantially improves the volume capacity of the base adsorbent and the capacity of the fuel storage tank. The present disclosure also relates to the overall shape and / or shape of the high density tangible of the mixed adsorbent to maximize the internal container / vessel volume of the gas storage system. The overall shape and / or shape of these types are shaped to minimize binder dilution, while maximizing component performance.

Where a range of values is provided, between the upper and lower limits of the range, each intermediate value up to 1/10 of the lower limit of the unit (e.g., In the case of a group, the number of each carbon atom within the range is provided), and any other stated or intermediate value within the stated range is understood to be encompassed within the present invention. The upper and lower limits of these smaller ranges can be independently included in smaller ranges and are also encompassed within the invention by applying any specifically excluded limit within the ranges provided. The ranges disclosed include one or both of the limits, and ranges excluding either or both of these included limits are also encompassed by the present invention.

The following terms are used to describe the present disclosure. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs unless otherwise defined. The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting of the invention.

The singular presentation as used herein and in the appended claims is intended to be used herein to refer to one or more (i. E., At least one) of the grammatical object of the article, unless the context clearly dictates otherwise. do. By way of example, " one element " means one element or more than one element.

As used herein and in the appended claims, the phrase " and / or " means a combined element, that is, either or both of the elements present in combination in some cases and separately present in other cases . The plural elements recited as " and / or " should be construed in the same manner, i.e., as " one or more " Any element other than those specifically identified by the " and / or " clause may optionally exist, whether or not related to the specifically identified element. Thus, as a non-limiting example, when used in connection with an open-end language such as " comprising ", referring to " A and / or B " (Optionally including non-B elements); In another embodiment B alone (including any non-A element); Yet another embodiment includes both A and B (optionally including other elements); And so on.

As used in the specification and claims, " or " should be understood to have the same meaning as " and / or " as defined above. For example, when separating an article from a list, the term " or " or " and / or " includes, that is, a list of elements or any number of elements, It will be interpreted to include more than one. On the contrary, unless the context clearly dictates otherwise, such as "exactly one" or "exactly one of," or in the claims, the term "consisting of" Will refer to including one element. In general, the term " or " as used herein refers to an exclusionary selection expression (i. E., If an exclusion term is preceded by " any one, " "Quot; one or the other but not all ").

In the claims, as well as in the specification, the terms "comprising," "including," "carrying," "having," "containing, involving, "" holding, "" composed of, "and the like are to be understood as being open-ended, ie, including but not limited to. Only "consisting of" and "consisting essentially of" linkages are provided for each closed closure or semi-closure, as set forth in Section 2111.03 of the United States Patent and Trademark Office, It is a connector.

As used in this specification and claims, the phrase " at least one, " in referring to the list of one or more elements means at least one element selected from any one or more elements in the list of elements, And does not exclude any combination of elements within the list of elements. This definition is also not related to or specifically related to the identified element, and allows elements other than those specifically identified in the list of elements to which the phrase " at least one " refers. Thus, as a non-limiting example, "at least one of A and B" (or equivalently, "at least one of A or B," or equally, "at least one of A and / At least one with no B and optionally including more than one A (and optionally including non-B elements); In another embodiment at least one that does not have A and optionally includes more than one B (and optionally includes non-A elements); And in yet another embodiment at least one, optionally including more than one, and optionally including more than one (and optionally including other elements); And so on.

It is also to be understood that in the specific methods described herein that involve more than one step or act, the order of steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are expressed, unless the context expressly indicates otherwise do.

According to one aspect, the present disclosure provides a method of storing gas. The method includes contacting the gas with at least one porous gas sorbent monolith having a working gravity capacity of? 40 lbs / GGE and / or a volume capacity of less than 35 L / GGE. The porous gas adsorbent monolith may have a part density of at least 0.4 g / cc. In certain embodiments, the working gravity capacity is ≦ 30 lbs / GGE (eg, ≦ 28 lbs / GGE) and / or the volume capacity is ≦ 32 L / GGE (eg, ≦ 30 L / GGE).

As used in this specification and the claims, the term " monolith " should be understood to include the formed adsorbent structures described herein and functional fragments thereof.

In some embodiments, the porous gas adsorbent monolith can be a gas adsorbent material (e.g., at least one of activated carbon, zeolite, silica, covalent organic framework, or metal organic framework) and a non-aqueous binder Polymers, polyamides, polyimides, high-performance plastics, fibrillated celluloses, copolymers with fluoropolymers, copolymers with polyamides, copolymers with polyimides, copolymers with high- Combinations thereof). In any aspect or embodiment described herein, the non-aqueous binder described herein is a fusing agent / binder. The fluoropolymer may be selected from the group consisting of poly (vinylidene difluoride), polytetrafluoroethylene, perfluoroalkoxyalkane, and fluorinated ethylene propylene. In any aspect or embodiment described herein, the non-aqueous binder of the present invention of the present disclosure is polytetrafluoroethylene or a derivative thereof. The polyamide may be selected from the group consisting of nylons (e.g., nylon-6,6 'and nylon-6). In any aspect or embodiment described herein, the non-aqueous binder of the present disclosure fuses to at least a portion of the components of the monolith / mixture. The polyimide may be selected from the group consisting of dianhydride polymer precursors. High-performance plastics may be selected from the group consisting of polyphenylene sulfide, polyketone, polysulfone, and liquid crystal polymers. In certain embodiments, the non-aqueous binder is present in an amount of up to 15 wt% and / or the gas adsorbing material is present in an amount of at least 85 wt%. The activated carbon may be derived from wood, peat moss, coconut shells, coal, walnut shells, synthetic polymers and / or natural polymers and / or may have a BET surface of at least about 1800 m ² / g. In one embodiment, the activated carbon is thermally activated, chemically activated, or a combination thereof.

In one aspect, the present disclosure provides a highly adsorptive monolith article comprising a gas adsorbing material and a non-aqueous binder as described in this disclosure. In one embodiment, the monolith has at least one of the following: a part density of at least 0.4 g / cc; Working weight capacity less than 40 lbs / GGE; Volume capacity less than 35 L / GGE; The gas sorbent material is present in an amount of at least 90 wt% (e.g., at least 92 wt% or at least 93 wt%); The non-aqueous binder is present in an amount less than 10 wt% (e.g., from about 2.5 wt% to about 7 wt% or 7 wt% or less); Or a combination thereof.

In another aspect, the present disclosure provides a highly adsorptive monolith article comprising a gas adsorbent material, wherein the monolith has a working weight capacity of less than 40 lbs / GGE and / or a volume capacity of less than 35 L / GGE. Moreover, the monolith may have a part density of at least 0.4 g / cc. In another embodiment, the monolith further comprises a non-aqueous binder, as described herein. For example, in any aspect or embodiment described herein, the non-aqueous binder of the present disclosure is polytetrafluoroethylene, or is derived therefrom.

In any of the aspects or embodiments described herein, the adsorbent monolith has: a volume of about 100 cc / L-M at a pore size of about 9 A or smaller than the diameter; About < RTI ID = 0.0 > 200 cc / L-M &lt; / RTI > volume at a pore size of about 9-27A or diameter; About 50 cc / L-M volume at a pore size of about 27-490 ANGSTROM or diameter; Or a combination thereof. For example, a pore size of about 9-27 ANGSTROM of the monolith or article may be> about 200 cc / LM,> about 210 cc / LM,> about 220 cc / LM,> about 230 cc / LM,> about 240 cc / ,> About 250 cc / LM,> about 260 cc / LM,> about 270 cc / LM, or> 275 cc / LM. Pores of less than about 9 Å of the monolith or article can have a volume of about 100 cc / LM, about 98 cc / LM, about 95 cc / LM, about 90 cc / LM, or about 85 cc / have. A pore size of about 27-490 A of the monolith or article may have a pore volume of> about 50 cc / L-M,> about 55 cc / L-M,> about 60 cc / L-M or> about 65 cc / L-M.

In one embodiment, the non-aqueous binder of the present disclosure includes a fluoropolymer (e.g., poly (vinylidene difluoride), polytetrafluoroethylene, perfluoroalkoxyalkane, or fluorinated ethylene propylene), polyamide (E.g., nylon-6,6 'or nylon-6), polyamides, high performance plastics (e.g., polyphenylene sulfide), copolymers with fluoropolymers, copolymers with polyamides, A copolymer of high-performance plastics, or a combination thereof. In certain embodiments, the non-aqueous binder of the composition of the present disclosure is present in an amount up to 10 wt%. For example, the non-aqueous binder of the composition of the present disclosure may contain from about 2.5 to about 10 wt%, from about 5.0 to about 10 wt%, from about 7.5 wt% to about 10 wt%, from about 9 to about 10 wt% About 2.5 wt% to about 7 wt%, about 2.5 wt% to about 5.0 wt%, or about 2.5 wt% to about 8 wt%, about 5.0 wt% to about 8 wt%, about 6.5 wt% to about 8 wt% And may be present in an amount of 2.5 wt% or less. In certain embodiments, the non-aqueous binder comprises about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3 wt%, about 4 wt% , About 5 wt%, about 5.5 wt%, about 6 wt%, about 6.5 wt%, about 7 wt%, about 7.5 wt%, about 8 wt%, about 8.5 wt%, about 9 wt%, about 9.5 wt% , Or about 10 wt%.

In some embodiments, the gas adsorbent material may comprise any suitable gas adsorbent material generally known in the art or known in the art. Those skilled in the art will recognize that particular types of gas adsorbent materials are particularly useful for gas sorbent monoliths, which are expressly contemplated herein. For example, in certain embodiments, the gas adsorbing material is at least one of activated carbon, zeolite, silica, a covalent organic framework, a metal organic framework, or a combination thereof. In certain embodiments, the gas adsorbing material is present in an amount of at least 90 wt%. For example, the gas adsorbent material may comprise at least 90 wt%, at least about 92.5 wt%, at least about 95 wt%, at least about 97 wt%, about 90.0 to about 99 wt%, about 92.5 wt% to about 99 wt% About 95.0 to about 97.5 wt.%, About 90.0 to about 95.0 wt.%, About 92.5 wt.% To about 95.0 wt.%, And about 95.0 wt.% To about 99.5 wt. , Or from about 90.0 to about 92.5 wt%. In certain embodiments, the gas adsorbent material comprises about 90 wt%, about 90.5 wt%, about 91 wt%, about 91.5 wt%, about 92 wt%, about 92.5 wt%, about 93 wt%, about 93.5 wt% About 94 wt%, about 95 wt%, about 95.5 wt%, about 96 wt%, about 96.5 wt%, about 97 wt%, about 97.5 wt%, about 98 wt%, about 98.5 wt% 99 wt%, or about 99.5 wt%.

In any of the aspects or embodiments described herein, the gas adsorbing material is in the form of a fine powder, e. G., Activated carbon. In any aspect or embodiment described herein, the gas adsorbing material is in granular form, e.g., activated carbon. Activated carbon is a non-graphitic microcrystal1ine form of carbon that has been processed into carbon particles with relatively high microporosity. Activated carbon is composed of a six-membered carbon ring with an amorphous carbon region therebetween. The activated carbon may contain residual oxygen, nitrogen, hydrogen, phosphorus, and / or compounds thereof. The International Union of Pure and Applied Chemistry classifies voids according to their width. Micropores include voids having a diameter or size less than about 2 nanometers (20 Angstroms). The mesopores include voids having a diameter or size of from about 2 to about 50 nanometers. A macropore is a pore with a diameter or size greater than 50 nanometers.

In a further embodiment, the gas adsorbent material is selected from the group consisting of nut shells, coconut shells, peat, wood, coir, lignite, coal, petroleum pitch, It is activated carbon.

In one embodiment, the activated carbon may have an average pore size ranging from about 0.8 nm (nanometer) to about 3.5 nm. In certain embodiments, the activated carbon may have an average pore size ranging from about 0.6 to about 2.6 nm. Activated carbon may have a minimum porosity greater than 6.0 nm. In some embodiments, the activated carbon has a particle size in the range of about 1.0 mu m (micron) to about 2.83 mm (millimeter). In certain embodiments, the activated carbon has a particle size in the range of about 5 [mu] m to about 120 [mu] m or about 15 [mu] m to about 120 [mu] m.

In certain embodiments, the activated carbon monolith has a supply volume of ≥ 0.5 cc / g (eg> 0.55 cc / g or 0.60 cc / g or> 0.60 cc / g) for pores in the size range of about 9 Å to about 27 Å. The pore volume is determined by nitrogen adsorption porosimetry using a Micoreeritics ASAP 2420 (Norcross, Ga.). Briefly, the sample / sample is dried overnight in a preset oven at 105-110 ° C. Until the temperature equilibrates with the laboratory, take the sample out and place it in a closed system. The sample is inserted into the instrument sample tube and placed on a Micromeritics ASAP 2420 instrument. The sample is degassed in-situ before starting the test. Degassing of the sample is carried out at a vacuum of 200 캜 and 2 탆 Hg. The data reported here can be collected in the degassed sample at temperatures below 200 ° C to prevent the binder from burning off. The determination of pore volume is calculated from the P / Po isotherm using the SAIEUS program. The non-ideality factor was 0.0000620. The density conversion factor was 0.0015468. The diameter of the hard-sphere was 3.860 Å. The molecular cross-sectional area was 0.162 nm2. The target relative pressures (mmHg) for the isotherms were: 0.002, 0.005, 0.01, 0.0125, 0.0250, 0.050, 0.075, 0.1, 0.1125, 0.125, 0.150, 0.175, 0.20, 0.25, 0.30, 0.40 , 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, and 0.95. At low pressure, the instrument is set to "low pressure incremental dose mode", instructing the instrument to record data based on an incremental dose of 20.0000 cm ^{3 /} g STP. Actual points were recorded with stricter values, either absolute or relative pressure tolerance of 5 mmHg or 5%, respectively. The time between successive pressure readings was 20 seconds at equilibrium. When? P between readings is < 0.001%, data was taken and P was set to the next set point. The minimum time delay between recorded data was 600 seconds. Nitrogen adsorption isotherm data were analyzed by the SAIEUS program. The " Max " field of the pore size range is changed to 500. On an L-curve chart, scroll the bar to set the lambda value to find the tangent point of the curve. The mathematical model for processing isotherm data obtained with Mieromeritics equipment to determine the pore size distribution is described by nonloeal density functional theory (NLDFT). This model is described in J. Phys. Chern., 2009, 113, 19382-19385, J. Jagiello and JP Olivier (same as small voids).

One type of activated carbon suitable for use in the practice of the present disclosure is Nuchar ^® SA-1500, Nuchar ^® WV-A 1500 and / or Nuchar ^® BAX 1500 from Ingevity ^® (North Charleston, SC, USA) And is commercially available. In certain embodiments, suitable activated carbons include coconut activated carbon and coal-based activated carbon.

In one embodiment, the monolith has a part density of at least 0.4 g / cc. For example, the part density of the monolith may range from about 0.40 g / cc to about 2.00 g / cc; From about 0.40 g / cc to about 1.50 g / cc; From about 0.40 g / cc to about 1.25 g / cc; From about 0.40 g / cc to about 1.00 g / cc; From about 0.40 g / cc to about 0.80 g / cc; About 0.40 g / cc to about 0.75 g / cc; From about 0.40 g / cc to about 0.65 g / cc; From about 0.40 g / cc to about 0.55 g / cc; From about 0.40 g / cc to about 0.55 g / cc; About 0.50 g / cc to about 2.00 g / cc; From about 0.50 g / cc to about 1.50 g / cc; About 0.50 g / cc to about 1.25 g / cc; About 0.50 g / cc to about 1.00 g / cc; From about 0.50 g / cc to about 0.75 g / cc; From about 0.60 g / cc to about 2.00 g / cc; From about 0.60 g / cc to about 1.50 g / cc; From about 0.60 g / cc to about 1.25 g / cc; From about 0.60 g / cc to about 1.00 g / cc; From about 0.70 g / cc to about 2.00 g / cc; From about 0.70 g / cc to about 1.50 g / cc; From about 0.70 g / cc to about 1.25 g / cc; From about 0.70 g / cc to about 1.00 g / cc; About 1.00 g / cc to about 2.00 g / cc; From about 1.00 g / cc to about 1.50 g / cc; From about 1.00 g / cc to about 1.25 g / cc; About 1.25 g / cc to about 2.00 g / cc; About 1.25 g / cc to about 1.50 g / cc; Or from about 1.50 g / cc to about 2.00 g / cc. In a specific embodiment, the part density is about 0.40 g / cc, about 0.4 g / cc, about 0.50 g / cc, about 0.55 g / cc, about 0.60 g / cc, about 0.65 g / cc, About 0.75 g / cc, about 0.80 g / cc, about 0.85 g / cc, about 0.90 g / cc, about 0.95 g / cc, about 1.00 g / cc, about 1.05 g / cc, about 1.10 g / Cc, about 1.25 g / cc, about 1.25 g / cc, about 1.30 g / cc, about 1.35 g / cc, about 1.40 g / cc, about 1.40 g / cc, about 1.60 g / cc, about 1.65 g / cc, about 1.70 g / cc, about 1.75 g / cc, about 1.80 g / cc, about 1.85 g / cc, about 1.90 g / , Or about 2.00 g / cc.

Part densities can be determined by any method known to those skilled in the art. For example, the density of a part can be determined by making a cylindrical part from the mixture and heating the part in an oven at &lt; RTI ID = 0.0 &gt; 110 C &lt; / RTI &gt; for 12 hours and measuring the mass. Diameter and length are determined by calipers. Divide the recorded mass by the calculated volume. In certain cases, the monolith is formed in the one-position, for example, that the molded monolith article dimensionally conforms to the inner dimensions of the container. The density of the particles is then determined by the internal volume of the container and the step of removing moisture as described above in the container, i.e. after heating the container containing the substance in the oven for &gt; It is measured by weight.

In certain embodiments, the monolith has a working weight capacity of less than 40 lbs / GGE. For example, the monolith may comprise: about 5 to about 40 lbs / GGE, about 10 to about 40 lbs / GGE, about 15 to about 40 lbs / GGE, about 20 to about 40 lbs / GGE, GGE, about 30 to about 40 lbs / GGE, about 35 to about 40 lbs / GGE, less than about 35 lbs / GGE, about 5 to about 35 lbs / GGE, about 25 to about 35 lbs / GGE, about 30 to about 35 lbs / GGE, about 30 lbs / GGE, about 5 to about 30 lbs / GGE, about 10 to about 35 lbs / About 25 to about 30 lbs / GGE, about 25 to about 30 lbs / GGE, about 15 to about 30 lbs / GGE, about 20 to about 30 lbs / From about 10 to about 25 lbs / GGE, from about 15 to about 25 lbs / GGE, from about 20 to about 25 lbs / GGE, from less than about 20 lbs / GGE, from about 5 to about 20 lbs / GGE, GGE, about 15 to about 20 lbs / GGE, less than about 15 lbs / GGE, about 5 to about 15 lbs / GGE, about 10 to about 15 lbs / GGE, or about 5 to about 10 lbs / It has a volume capacity. In certain embodiments, the working weight capacity of the monolith may be about 1 lbs / GGE, about 2 lbs / GGE, about 3 lbs / GGE, about 4 lbs / GGE, about 5 lbs / GGE, about 6 lbs / about 10 lbs / GGE, about 11 lbs / GGE, about 12 lbs / GGE, about 13 lbs / GGE, about 14 lbs / GGE, about 15 lbs / GGE, about 8 lbs / GGE, about 16 lbs / GGE, about 17 lbs / GGE, about 18 lbs / GGE, about 19 lbs / GGE, about 20 lbs / GGE, about 21 lbs / About 26 lbs / GGE, about 27 lbs / GGE, about 28 lbs / GGE, about 29 lbs / GGE, about 30 lbs / GGE, about 31 lbs / GGE, about 32 lbs / GGE, about 26 lbs / about 36 lbs / GGE, about 38 lbs / GGE, about 39 lbs / GGE, about 40 lbs / GGE, about 35 lbs / GGE, about 36 lbs / / GGE.

The weight capacity and reversible storage (or "reversible capacity") can be measured using a digital pressure readout, a digital temperature readout, and a 4- It is determined in the port sample holder system. A sample of known part density specially formed to closely fit the cylindrical sample holder is loaded into the pre-weighed sample holder. An internal thermocouple is located in the center of each sample holder to monitor and control the sample temperature during pressurization and depressurization. The sample is connected to the test equipment and degassed at 300 ° F under vacuum (24 mmHg) for a minimum of 3 hours. The sample is then cooled to room temperature and the vacuum is turned off. In the closed state, remove the sample holder and measure the weight again to obtain the sample weight. The sample is then pressurized to the desired pressure with probe gas (natural gas or methane). This proceeds slowly enough to prevent the internal temperature from increasing by more than 10.. When the desired pressure is obtained, the probe gas valve is closed. As the internal temperature decreases, the pressure inside the sample holder decreases. The probe gas valve opens slightly and the pressure increases again to the desired range. This is repeated. If the temperature is constant and there is no 0.1% pressure change over a 10 minute time interval, close the sample holder and measure the weight again to determine the amount of gas in the system. The sample holder is reconnected and the decompression step is started. A temperature gauge correlated to the sample's internal temperature is used to determine how quickly it is depressurized. The temperature of the sample should not fall faster than 10 ° F. If the pressure is ambient pressure and the temperature is a predetermined set point, the sample holder is again weighed to determine the amount of gas released. The weight (gram) of the gas released is determined by the weight difference. The volume occupied by the sample holder is determined by multiplying the sample weight by the particle density. The free space of the sample holder is then determined (which is calculated based on the difference between the theoretical sample weight (sample holder inner volume multiplied by the part density) and the actual sample weight), then the calculated free space the ideal gas equation the amount of gas, PV = znRT (n is a positive gas mole, z is the compression factor (compressibility factor) (for methane at 900 psi 0.87), P is the test pressure (atm), V = free, which accounts for The volume of space (cubic centimeters), T is the temperature (K), and R is the gas constant (82.05736 cm ³ atm K ^-1 mol ^-1 ). The weight of the gas remaining in the sample at 0 psig and of the free space gas is subtracted from the total weight of the stored gas at 900 psig. This value is divided by the weight of the sample to provide a gram of gas that is stored reversibly per gram of sample. Grams of reversibly stored gas are converted to GGE using the previously cited conversion factor (2567 g-NG per GGE, equivalent to 5.66 lb-NG / GGE) and the mass of the sample is converted from grams to pounds, The capacity is calculated as lb-monolith or -sample, or lb / GGE per GGE. The compressed natural gas blend for the tested absorption capacity was 94.5% methane, 2.8% ethane, 0.3% propane, 0.1% butane, <0.5% other hydrocarbons (total), 0.9% nitrogen, and 0.9% CO _It was obtained from Gas Innovations (La Porte TX; www.gasinnovations.com) in smelly form with an analysis certificate of ₂ .

In a further embodiment, the monolith has a volume performance of less than 35 L / GGE. For example, the volumetric performance can range from about 15 L / GGE to about 35 L / GGE, from about 17 L / GGE to about 35 L / GGE, from about 19 L / GGE to about 35 L / About 35 L / GGE, about 23 L / GGE to about 35 L / GGE, about 25 L / GGE to about 35 L / GGE, about 27 L / About 35 L / GGE, about 35 L / GGE, about 35 L / GGE, about 33 L / GGE to about 35 L / GGE, about 15 L / GGE, about 32 L / GGE, about 32 L / GGE, about 21 L / GGE to about 32 L / GGE, about 23 L / About 27 L / GGE to about 32 L / GGE, about 29 L / GGE to about 32 L / GGE, about 15 L / GGE to about 29 L / GGE, about 17 L / From about 23 L / GGE to about 29 L / GGE, from about 25 L / GGE to about 29 L / GGE, from about 21 L / GGE to about 29 L / About 26 L / GGE, about 17 L / GGE to about 26 L / GGE, about 19 L / GGE to about 26 L / GGE, about 21 L / From about 15 L / GGE to about 23 L / GGE, from about 17 L / GGE to about 23 L / GGE, from about 19 L / GGE to about 23 L / GGE, from about 15 L / 20 L / GGE, about 17 L / GGE to about 20 L / GGE, or about 15 L / GGE to about 17 L / GGE. In certain embodiments, the monolith has a volumetric performance of about 35 L / GGE, about 34 L / GGE, about 33.5 L / GGE, about 33 L / GGE, about 32.5 L / About 29 L / GGE, about 28 L / GGE, about 28 L / GGE, about 27.5 L / GGE, about 30 L / GGE, about 30 L / About 25 L / GGE, about 24 L / GGE, about 24 L / GGE, about 23.5 L / GGE, about 23 L / GGE, about 26 L / About 18 L / GGE, about 22 L / GGE, about 21 L / GGE, about 20 L / GGE, about 19 L / GGE, about 18 L / GGE, or about 15 L / GGE.

In any aspect or embodiment described herein, the adsorptive monolith of this disclosure comprises a gas adsorbent material (e.g., activated carbon) present in an amount of at least 90 wt% (e.g., at least 93 wt% (E.g., from about 2.5 wt% to about 7 wt%, from about 3 wt% to about 7 wt%, ≦ 7.5 wt%, or ≦ 7 wt%) of the polytetrafluoroethylene Ethylene, and the monolith has one of the following: a working weight capacity of ≤ 40 lbs / GGE (eg, ≤ 35 lbs / GGE, ≤ 30 lbs / GGE, or ≤ 28 lbs / GGE); (E.g., from about 0.40 g / cc to about 0.75 g / cc, about 0.4 g / cc), a volume performance of at least 0.4 g / cc / cc to about 0.65 g / cc, or from about 0.4 g / cc to about 0.6 g / cc), the pore volume of the pores having a size ranging from about 9 A to about 27 A is at least 0.5 cc / g, or a combination thereof.

The activated carbon monoliths described herein are highly adsorptive, monolith articles designed to be shape-specific. The non-aqueous binders described herein significantly increase the packing density of the adsorbent compared to conventional packed adsorbents. As a result, the porous gas sorbent monoliths of this disclosure provide significantly improved working weight capacity and volume capacity. Moreover, the use of shape-specific monolith articles simplifies the manufacture of gas storage systems, since the gas adsorbent material can be handled in monolithic form. In some embodiments, the mixed material, which may optionally be dried, may be preformed in a gas storage system. For example, the mixed material may be located in a gas storage system in which the mixed material is compressed. In addition, the compressed and mixed material can be heated.

According to another aspect, the present disclosure provides a method for manufacturing a porous gas adsorbent monolith 60, as shown in FIG. The method includes the steps of (62) mixing a gas adsorbing material and a non-aqueous binder, as described herein; And compressing or extruding the mixture (64) into a forming structure. The mixture may be mixed by any suitable method known in the art or known in the art. For example, the mixer may be selected from the group consisting of a muller, a plow, a blender, a kneader, an extruder and a pin mixer. In certain embodiments, the mixing step 62 may be performed for at least about 10 minutes (e.g., at least about 15 minutes, at least about 20 minutes, at least about 25 minutes, about 10-45 minutes, about 10-35 minutes, , 10-15 minutes or less). The method may further comprise drying the mixture before compressing or extruding the mixture. For example, the method may further comprise drying the mixture at a temperature of at least 110 &lt; 0 &gt; C. The mixture can be heated during compression. For example, the method may further include heating (64) the compressed mixture at a temperature of at least about 110 캜 (e.g., from about 110 캜 to about 400 캜). In one embodiment, the porous gas adsorbent monolith is fabricated in a gas storage tank / system. This is explained in detail below.

In another embodiment, the porous gas adsorbent monolith is formed in a gas storage system. For example, a method of making a porous gas adsorbent monolith comprises mixing a gas adsorbing material and a non-aqueous binder as described herein; Placing the mixture in a gas storage tank; And compressing the mixture in a gas storage tank. In another embodiment, the method further comprises heating the compressed mixture in a gas storage tank. It is mentioned that each of these steps of the process can be carried out as described herein for a method not related to producing a porous gas adsorbent monolith in a gas storage system / tank. For example, the mixture may comprise a mixer, which may be selected from the group consisting of muller, plow, blender, kneader, extruder and pin mixer, May be mixed by any suitable method known in the art or known in the art. Mixing can occur within a period of 10-15 minutes. The method may further comprise drying the mixture before compressing the mixture. For example, the method may further comprise drying the mixture at a temperature of at least 110 &lt; 0 &gt; C. The dried mixture can be compressed into the reverse shape of the next outer tank located inside the gas storage system / tank. The mixture may be heated to at least about 110 캜 (i.e., from about 110 캜 to about 400 캜) during compression.

The amount and properties of the gas adsorbing material and the non-aqueous binder of the above method are described above in connection with the implementation of activated carbon monoliths.

In any aspect or embodiment described herein, other agents are contemplated for the manufacture of monoliths (e.g., emulsifiers, rheology aids, thickeners, surfactants, and dispersion aids).

Dispersion aids can be used to impart better particle stability to prevent binder-binder aggregation, carbon-carbon aggregation, and agglomeration of the mixture. The dispersant may impart electrostatic, steric, and / or other stabilizations to the binder. The dispersing agent may comprise any suitable dispersing agent generally known or known in the art. For example, suitable dispersants include stearates, polyethylene glycols, monostearates, distearates, polycarboxylic acids, polyethers, and block copolymers.

Thickening agents can be used to impart greater fluidity to the mixture. In any of the aspects or embodiments described herein, the method further comprises adding a thickener to the activated carbon. The thickening agent may comprise any suitable thickening agent generally known or known in the art. For example, suitable thickening agents include water-soluble polymers such as methylcellulose, methylcellulose ether, and polyacrylic acid.

The rheology agent (s) may be used to control the rheological properties of the pre-wet activated carbon or mixture. In particular, this adjustment may be required depending on the molding method. Extrusion, for example, requires the same consistency as a gel. In certain embodiments, the method further comprises adding a thickening agent to the mixture. The thickening agent may comprise any suitable thickening agent generally known or known in the art, as described above.

In certain embodiments, the method further comprises adding a thinning agent to the mixture. The diluent may include any suitable diluent commonly known or known in the art. For example, the diluent may be a surfactant such as anionic, cationic, and nonionic surfactants. Examples of anionic surfactants include, but are not limited to, carboxylates, phosphates, sulfonates, sulfates, sulfoacetates, and the free acids of these salts. Cationic surfactants include salts of long chain amines, diamines and polyamines, quaternary ammonium salts, polyoxyethylenated long chain amines, long chain alkylpyridinium salts and lanolin quaternary salts and the like. Nonionic surfactants include, but are not limited to, long chain alkylamine oxides, polyoxyethylenated alkylphenols, polyoxyethylenated straight and branched chain alcohols, alkoxylated lanolin waxes, polyglycol esters, lignosulfate derivatives, octophenol, nonylphenol, polyethylene glycol mono Ether, dodecylhexaoxylene glycol monoether, naphthalene sulfonate, trisodium phosphate, sodium dodecylsulfate, sodium lauryl sulfate, and the like. The specific amount of surfactant used will vary and will be known to those skilled in the art. For example, in one embodiment, the diluent is present in an amount sufficient to form an extrudable mixture in the mixture.

In any aspect or embodiment described herein, the mixture may be compressed or extruded 64 into a mold or gas storage system / tank, without heating or heating the molding structure, to form a mold (i.e., a molded structure) System / tank or extrusion. That is, to form the desired shape of the activated carbon monolith, the mixture may be cast in a mold or placed in a gas storage tank / system. In certain embodiments, the pressure applied to the mold or vapor storage tank / system with the mixture is at least 1,250 psi, at least 1,500 psi, at least 3,000 psi, at least 5,000 psi, at least 7,500 psi, at least 10,000 psi, at least 12,500 psi, 15,000 psi, at least 30,000 psi, or at least 10,000 psi. For example, the pressure applied to the mold may be from about 1,250 psi to about 60,000 psi; About 1,250 psi to about 40,000 psi; About 1,250 psi to about 35,000 psi; From about 1,250 psi to about 30,000 psi; About 1,250 psi to about 25,000 psi; About 1,250 psi to about 20,000 psi; About 1,250 psi to about 15,000 psi; From about 1,250 psi to about 10,000 psi; About 1,250 psi to about 7,500 psi; From about 3,000 psi to about 60,000 psi; From about 3,000 psi to about 40,000 psi; From about 3,000 psi to about 35,000 psi; From about 3,000 psi to about 30,000 psi; From about 3,000 to about 25,000 psi; From about 3,000 psi to about 20,000 psi; From about 3,000 psi to about 15,000 psi; From about 3,000 psi to about 10,000 psi; From about 3,000 psi to about 7,500 psi; From about 5,000 psi to about 60,000 psi; From about 5,000 psi to about 40,000 psi; From about 5,000 psi to about 35,000 psi; From about 5,000 psi to about 30,000 psi; From about 5,000 psi to about 25,000 psi; From about 5,000 psi to about 20,000 psi; From about 5,000 psi to about 15,000 psi; From about 5,000 psi to about 10,000 psi; From about 5,000 psi to about 7,500 psi; From about 6,000 psi to about 60,000 psi; From about 6,000 psi to about 40,000 psi; From about 6,000 psi to about 35,000 psi; From about 6,000 psi to about 30,000 psi; From about 6,000 psi to about 25,000 psi; From about 6,000 psi to about 20,000 psi; From about 6,000 psi to about 15,000 psi; From about 6,000 psi to about 10,000 psi; From about 6,000 psi to about 7,500 psi; From about 7,000 psi to about 60,000 psi; From about 7,000 psi to about 40,000 psi; From about 7,000 psi to about 35,000 psi; From about 7,000 psi to about 30,000 psi; About 7,000 psi to about 25,000 psi; From about 7,000 psi to about 20,000 psi; From about 7,000 psi to about 15,000 psi; From about 7,000 psi to about 10,000 psi; From about 8,000 psi to about 60,000 psi; From about 8,000 psi to about 40,000 psi; From about 8,000 psi to about 35,000 psi; From about 8,000 psi to about 30,000 psi; From about 8,000 psi to about 25,000 psi; From about 8,000 psi to about 20,000 psi; From about 8,000 psi to about 15,000 psi; From about 8,000 psi to about 10,000 psi; From about 10,000 psi to about 60,000 psi; From about 10,000 psi to about 40,000 psi; From about 10,000 psi to about 35,000 psi; From about 10,000 psi to about 30,000 psi; From about 10,000 psi to about 25,000 psi; From about 10,000 psi to about 20,000 psi; From about 10,000 psi to about 15,000 psi; From about 15,000 psi to about 60,000 psi; From about 15,000 psi to about 40,000 psi; From about 15,000 psi to about 35,000 psi; From about 15,000 psi to about 30,000 psi; From about 15,000 psi to about 25,000 psi; From about 15,000 psi to about 20,000 psi; From about 20,000 psi to about 60,000 psi; From about 20,000 psi to about 40,000 psi; From about 20,000 psi to about 35,000 psi; From about 20,000 psi to about 30,000 psi; From about 20,000 psi to about 25,000 psi; From about 25,000 psi to about 60,000 psi; From about 25,000 psi to about 40,000 psi; From about 25,000 psi to about 35,000 psi; From about 25,000 psi to about 30,000 psi; From about 30,000 psi to about 60,000 psi; From about 30,000 psi to about 50,000 psi; From about 30,000 psi to about 40,000 psi; From about 30,000 psi to about 35,000 psi; From about 35,000 psi to about 60,000 psi; From about 35,000 psi to about 50,000 psi; From about 35,000 psi to about 45,000 psi; From about 35,000 psi to about 40,000 psi; From about 40,000 psi to about 60,000 psi; Or from about 40,000 psi to about 45,000 psi. In another embodiment, the mixture is extruded into the desired shape with any known, commercially available extruder. It is understood that the activated carbon monolith may be formed in any desired shape, for example, a cylinder, an egg-shaped prism, a cube, an elliptical prism, a right-angled prism, a pentagonal prism, or even an irregular three-dimensional shape.

The activated carbon monolith has a width / diameter of at least 1 inch, at least 2 inches, at least 3 inches, at least 4 inches, at least 5 inches, at least 6 inches, at least 7 inches, at least 8 inches, or at least 9 inches Such as a desired shape, circle, oval, square, rectangular, elliptical, pentagonal, irregular shape, etc.). For example, the monolith may be about 1 inch to about 10 inches, about 1 inch to about 9 inches, about 1 inch to about 8 inches, about 1 inch to about 7 inches, about 1 inch to about 6 inches, About 2 inches to about 8 inches, about 2 inches to about 7 inches, about 2 inches to about 6 inches, about 5 inches, about 1 inches to about 4 inches, about 2 inches to about 10 inches, From about 2 inches to about 4 inches, from about 3 inches to about 10 inches, from about 3 inches to about 9 inches, from about 3 inches to about 8 inches, from about 3 inches to about 7 inches, From about 3 inches to about 6 inches, from about 3 inches to about 5 inches, from about 3 inches to about 4 inches, from about 4 inches to about 10 inches, from about 4 inches to about 9 inches, from about 4 inches to about 8 inches, About 4 inches to about 6 inches, about 4 inches to about 5 inches, about 5 inches to about 10 inches, about 5 inches About 9 inches, about 5 inches to about 8 inches, about 5 inches to about 7 inches, about 7 inches to about 10 inches, or about 7 inches to about 9 inches. The thickness of the activated carbon monolith is from about 0.1 inch to about 3 inch, from about 0.1 inch to about 2.5 inch, from about 0.1 inch to about 2.0 inch, from about 0.1 inch to about 1.5 inch, from about 0.1 inch to about 1.0 inch, About 0.25 inches to about 2.5 inches, about 0.25 inches to about 3 inches, about 0.25 inches to about 2.5 inches, about 0.25 inches to about 2.0 inches, about 0.25 inches to about 1.5 inches, about 0.25 inches to about 1.0 inches, About 0.5 inches to about 3 inches, about 0.5 inches to about 2.5 inches, about 0.5 inches to about 2.0 inches, about 0.5 inches to about 1.5 inches, about 0.5 inches to about 1.0 inches, about 0.75 inches to about 3 inches About 0.75 inch to about 2.5 inch, about 0.75 inch to about 2.0 inch, about 0.75 inch to about 1.5 inch, about 0.75 inch to about 1.0 inch, about 1 inch to about 3 inch, about 1 inch to about 2.5 inch, 1 inch to about 2.0 inches, about 1 From about 1.5 inches to about 3 inches, from about 1.5 inches to about 2.5 inches, from about 1.5 inches to about 2.0 inches, from about 2 inches to about 3 inches, from about 2 inches to about 2.5 inches, May be in the range of about 3 inches.

In any aspect or embodiment described herein, the method further comprises heating the mixture before compressing or extruding the mixture. In some embodiments, the heating prior to compression or extrusion is performed at a temperature of from about 100 占 폚 to about 300 占 폚, from 100 占 폚 to about 290 占 폚, from 100 占 폚 to about 280 占 폚, from 100 占 폚 to about 270 占 폚, About 100 deg. C to about 200 deg. C, about 100 deg. C to about 190 deg. C, about 100 deg. C to about 240 deg. From about 100 占 폚 to about 180 占 폚, from about 100 占 폚 to about 170 占 폚, from about 100 占 폚 to about 160 占 폚, from about 100 占 폚 to about 140 占 폚, from 110 占 폚 to about 300 占 폚, From about 110 ° C to about 250 ° C, from about 110 ° C to about 250 ° C, from about 110 ° C to about 230 ° C, from about 110 ° C to about 220 ° C, from about 110 ° C to about 210 ° C, From about 10 C to about 200 C, from about 10 C to about 190 C, from about 10 C to about 180 C, from about 10 C to about 170 C, from about 10 C to about 160 C, from 120 C to about 300 C, 120 deg. C to about 280 deg. C, 120 deg. C About 120 ° C to about 200 ° C, about 120 ° C to about 260 ° C, about 120 ° C to about 250 ° C, 120 ° C to about 230 ° C, About 120 ° C to about 190 ° C, about 120 ° C to about 180 ° C, about 120 ° C to about 170 ° C, about 120 ° C to about 160 ° C, 130 ° C to about 300 ° C, 130 ° C to about 290 ° C, 130 ° C to about 250 ° C, about 130 ° C to about 250 ° C, 130 ° C to about 230 ° C, about 130 ° C to about 220 ° C, From about 130 ° C to about 180 ° C, from about 130 ° C to about 170 ° C, from 140 ° C to about 300 ° C, from 140 ° C to about 290 ° C, from 140 ° C to about 280 ° C From about 140 DEG C to about 220 DEG C, from about 140 DEG C to about 220 DEG C, from about 140 DEG C to about 270 DEG C, from 140 DEG C to about 260 DEG C, from about 140 DEG C to about 250 DEG C, About 200 &lt; 0 &gt; C, about 140 &lt; 0 &gt; C to about 190 & About 150 deg. C to about 280 deg. C, about 150 deg. C to about 260 deg. C, about 150 deg. C to about 250 deg. About 150 ° C to about 190 ° C, about 150 ° C to about 220 ° C, about 150 ° C to about 220 ° C, about 150 ° C to about 210 ° C, 160 ° C to about 280 ° C, 160 ° C to about 270 ° C, 160 ° C to about 260 ° C, about 160 ° C to about 180 ° C, about 150 ° C to about 170 ° C, About 160 DEG C to about 230 DEG C, about 160 DEG C to about 220 DEG C, about 160 DEG C to about 220 DEG C, about 160 DEG C to about 200 DEG C, about 160 DEG C to about 190 DEG C, About 180 deg. C to about 250 deg. C, about 180 deg. C to about 300 deg. C, 180 deg. C to about 290 deg. 230 deg. C, from about 180 deg. C to about 220 deg. C, from about 180 deg. C to about 210 deg. From about 200 ° C to about 250 ° C, from about 200 ° C to about 250 ° C, from about 200 ° C to about 300 ° C, from 200 ° C to about 290 ° C, from 200 ° C to about 280 ° C, At a temperature range of from about 200 캜 to about 230 캜, from 230 캜 to about 290 캜, from 230 캜 to about 280 캜, from 230 캜 to about 270 캜, from 230 캜 to about 260 캜, do. In other embodiments, the drying prior to compression or extrusion of the mixture may be performed at a temperature of about 100 캜, about 105 캜, about 110 캜, about 115 캜, about 120 캜, about 125 캜, about 130 캜, about 135 캜, About 145 DEG C, about 150 DEG C, about 155 DEG C, about 160 DEG C, about 165 DEG C, about 170 DEG C, about 175 DEG C, about 180 DEG C, about 185 DEG C, about 190 DEG C, about 195 DEG C, About 250 ° C, about 260 ° C, about 265 ° C, about 260 ° C, about 210 ° C, about 215 ° C, about 220 ° C, about 225 ° C, about 230 ° C, about 235 ° C, About 270 DEG C, about 275 DEG C, about 280 DEG C, about 285 DEG C, about 290 DEG C, about 295 DEG C, or about 300 DEG C.

In any aspect or embodiment described herein, the method further comprises heating (64) the shaped mixture. In some embodiments, the mixture is heated to a temperature of from about 110 캜 to about 270 캜, from about 110 캜 to about 250 캜, from 110 캜 to about 230 캜, from about 110 캜 to about 220 캜, About 120 DEG C to about 250 DEG C, about 120 DEG C to about 230 DEG C, about 120 DEG C to about 220 DEG C, and about 200 DEG C, about 110 DEG C to about 180 DEG C, , About 120 ° C to about 210 ° C, about 120 ° C to about 200 ° C, about 120 ° C to about 180 ° C, about 120 ° C to about 160 ° C, about 130 ° C to about 270 ° C, About 130 ° C to about 220 ° C, about 130 ° C to about 210 ° C, about 130 ° C to about 200 ° C, about 130 ° C to about 180 ° C, about 140 ° C to about 270 ° C, About 140 ° C to about 220 ° C, about 140 ° C to about 220 ° C, about 140 ° C to about 210 ° C, about 140 ° C to about 200 ° C, about 140 ° C to about 180 ° C, About 150 &lt; 0 &gt; C to about 250 &lt; 0 &gt; C, About 150 ° C to about 220 ° C, about 150 ° C to about 210 ° C, about 150 ° C to about 200 ° C, about 150 ° C to about 180 ° C, about 160 ° C to about 270 ° C, About 160 DEG C to about 200 DEG C, about 160 DEG C to about 230 DEG C, about 160 DEG C to about 220 DEG C, about 160 DEG C to about 210 DEG C, about 160 DEG C to about 200 DEG C, About 200 DEG C to about 250 DEG C, about 200 DEG C to about 230 DEG C, about 220 DEG C to about 250 DEG C, about 180 DEG C to about 230 DEG C, about 180 DEG C to about 210 DEG C, Deg.] C to about 270 [deg.] C, or from about 220 [deg.] C to about 250 [deg.] C. In other embodiments, the drying is performed at about 110 캜, about 120 캜, about 125 캜, about 130 캜, about 135 캜, about 140 캜, about 145 캜, about 150 캜, about 155 캜, About 170 DEG C, about 175 DEG C, about 180 DEG C, about 185 DEG C, about 190 DEG C, about 195 DEG C, about 200 DEG C, about 205 DEG C, about 210 DEG C, about 215 DEG C, about 220 DEG C, 230 ° C, about 240 ° C, about 250 ° C, about 260 ° C, or about 270 ° C.

According to another aspect of the present disclosure, as shown in Figure 3, a gas storage system 10 is disclosed herein. The system includes an envelope or container 20 (i.e., a vessel or tank) and a microporous or nanoporous monolithic carbonaceous article (i.e., a porous gas adsorbent monolith or activated carbon monolith) 30 of the present disclosure, For example, a gas adsorbing material and a non-aqueous binder, as described. In certain embodiments, the container is configured to withstand a pressure of at least 1,000 psi.

In certain embodiments, the envelope or container defines a body having an internal dimension and an internal volume. In certain embodiments, the formed adsorbent constitutes about 80% to about 99.9% of the inner volume of the envelope or container. For example, the formed adsorbent can comprise from about 70 to about 99%, from about 70 to about 95%, from about 70 to about 90%, from about 70 to about 85%, from about 70% to about 80% From about 75% to about 99%, from about 75% to about 99%, from about 75% to about 95%, from about 75% to about 90% , About 80 to about 95%, about 80 to about 90%, about 85% to about 99.9%, about 85 to about 99%, about 85 to about 95%, about 90% to about 99.9% %, About 90% to about 95%, about 95% to about 99.9%, about 95% to about 99%. In certain embodiments, the container is a tank.

In any aspect or embodiment described herein, the container 20 may comprise any suitable container generally known or known in the art. In certain embodiments, the container 20 may be made of any material suitable for reusable pressure vessels rated at service pressures of up to about 1,800 psi. In one embodiment, the pressure vessel is rated at an operating pressure in the range of about 250 psi to about 1,800 psi, and more specifically, about 450 psi to about 1,000 psi. Alternatively, the pressure vessel may comprise: from about 250 psi to about 1800 psi; From about 250 psi to about 1,700 psi; From about 250 psi to about 1600 psi; From about 250 psi to about 1,500 psi; From about 250 psi to about 1400 psi; From about 250 psi to about 1,300 psi; From about 250 psi to about 1200 psi; From about 250 psi to about 1,100 psi; From about 250 psi to about 1,000 psi; From about 250 psi to about 900 psi; From about 350 psi to about 1800 psi; From about 350 psi to about 1,700 psi; From about 350 psi to about 1600 psi; From about 350 psi to about 1,500 psi; From about 350 psi to about 1400 psi; From about 350 psi to about 1,300 psi; From about 350 psi to about 1,200 psi; From about 350 psi to about 1,100 psi; From about 350 psi to about 1,000 psi; From about 350 psi to about 900 psi; From about 450 psi to about 1800 psi; About 450 psi to about 1,700 psi; From about 450 psi to about 1600 psi; From about 450 psi to about 1,500 psi; From about 450 psi to about 1400 psi; From about 450 psi to about 1,300 psi; About 450 psi to about 1,200 psi; From about 450 psi to about 1,100 psi; From about 450 psi to about 1,000 psi; From about 450 psi to about 900 psi; From about 550 psi to about 1800 psi; From about 550 psi to about 1,700 psi; From about 550 psi to about 1600 psi; From about 550 psi to about 1,500 psi; From about 550 psi to about 1400 psi; From about 550 psi to about 1,300 psi; From about 550 psi to about 1,200 psi; From about 550 psi to about 1,100 psi; From about 550 psi to about 1,000 psi; Or from about 550 psi to about 900 psi. Examples of suitable container materials include high strength aluminum alloys (e.g., 7000 series aluminum alloys with relatively high yield strength), high strength low alloy (HSLA) steels (e.g., aluminum 7075-T6) as well as plastic or low strength aluminum alloys Strong polymeric fibers such as C-epoxy, glass fiber-polymer, Kevlar, Zylon, steel wire, belt, tape, metal coating or any similar reinforcing material, aluminum 6061-T6, long stranded or chopped carbon wraps fiber wraps, etc., and any combination thereof).

According to a particular embodiment, the desired porous gas adsorbent monolith 30 shape is one of a rectangular prism, a cylinder, or an egg-shaped prism. However, it is understood that the shape and size of the container 20 and the porous gas adsorbent monolith 30 may vary depending on the particular application. Further, although not shown, the container 20 may be configured with other containers such that a plurality of containers 20 are in fluid communication (e.g., gas) through a manifold or other suitable mechanism.

The porous gas adsorbent monolith (30) is placed in a container (20). As noted above, the monolith 30 can at least releasably retain a natural gas compound (i.e., reversibly store or adsorb and desorb gas molecules such as natural gas or methane). In some embodiments, the monolith 30 may also include other components found in natural gas such as other hydrocarbons (e.g., ethane, propane, hexane, etc.), hydrogen gas, carbon monoxide, carbon dioxide, nitrogen gas, and / Can be stored. In yet another embodiment, the monolith 30 can be inert to some of the natural gas components and can releasably hold other natural gas components.

In any aspect or implementation described herein, the system 10 further includes a device capable of charging and / or discharging the system. In a particular embodiment, the charging and / or discharging device is a port 30. It is understood that the device may be any suitable device generally known in the art or may be known to be capable of charging and / or discharging the system.

Example

Comparison of monoliths with non-aqueous binders and monoliths with aqueous binders

The reversible volumetric capacity and weight capacity of natural gas were investigated for three types of monoliths. The data are shown in Table 1 and Table 2. The monolith with an aqueous binder had a weight capacity ranging from about 34 to about 48 lb / GGE and a volume capacity ranging from about 25 to about 31 L / GGE range. Monoliths with non-aqueous binders described herein have an improved working weight capacity in the range of about 24 to about 30 lb / GGE and volume capacities in the range of about 23 to about 27 L / GGE.

Table 1. Specific properties of activated carbon used in the monolith embodiment

Example carbon Raw material company Total pore volume,
&Lt; 320 A (g / cc) NG pore volume,
9-27 A (g / cc) 1-3 Alkali activation sawdust Ingevity 1.14 0.78 4-5 PicaChem 8P Coconut shell Calgon 0.57 0.24 6-8 Nuchar® SA-1500 sawdust Ingevity 1.21 0.57

Table 2. Weight and volume capacity of activated carbon monoliths made of several types of activated carbon with non-aqueous or aqueous binders as described herein

Example type carbon bookbinder bookbinder
density
(wt%) Weight capacity
(lbs / GGE) Volume Capacity (L / GGE) * NG Pore volume fraction, (%) One Comparative Example Alkali activation CMC 10 36.4 25.4 0.83 2 A typical implementation Alkali activation PTFE 5 24.2 23.5 0.98 3 A typical implementation Alkali activation KYBLOCK 10 24.1 23.6 0.93 4 Comparative Example PicaChem 8P UHMWPE 15 48.6 33.7 0.89 5 Comparative Example PicaChem 8P CMC 12 48.4 30.8 0.85 6 Comparative Example Nuchar® SA-1500 CMC 10 31.9 27.2 0.80 7 Comparative Example Nuchar® SA-1500 UHMWPE 15 33.4 30.6 0.68 8 A typical implementation Nuchar® SA-1500 PTFE 5 27.6 26.1 0.94

*, The fraction of NG pore volume is the amount of NG pore volume of carbon in the resulting monolith, based on the absence of a binder for the NG pore volume of the starting component carbon .

Thus, the non-aqueous binders of the present disclosure demonstrate the ability to provide monoliths with superior working weight capacity and volume capacity as compared to monoliths made with aqueous binders. This is due to the better holding of the pore volume of 9-27 ANGSTROM from the component adsorbent in the final monolith by using the binders of this disclosure compared to the comparative binder, as shown in FIG.

Example 1: Alkali activated carbon combined with CMC. Alkaline activated carbon has been regarded as an excellent adsorbent for natural gas due to the considerable amount of pore volume in the micropore range (pore < 2 nm) and the amount of pore volume in the range of 9-27A, which is more importantly determined in this disclosure . The blend was prepared in a Simpson Muller mixer by adding alkali activated wood-based carbon and CMC together at the desired weight ratio (90 wt% carbon to 10 wt% carboxymethyl cellulose (CMC)). The mixer was treated to mix the ingredients for 5 minutes and then add water at a ratio of 1.7: 1 water to solids. Upon addition of water, the mixer was continued for an additional 35 minutes. A monolith was formed from the blend by compression molding with a 4 inch ID cylinder mold and 40 K psig and sufficient material to obtain a 0.75 inch thickness processed at room temperature and about 70.. Upon discharge, the monolith was stored at low temperature (<80 ° F) for 48 hours to minimize shrinkage, and then placed in a pre-set oven at 110 ° C and dried to evaporate the water remaining in the monolith. Using a hole saw with a 1.25 inch outer diameter, we made a larger, 4-inch monolithic core part. The performance of the material showed very high adsorption capacity and good (i.e. low) L / GGE volumetric capacity due to component carbon. The weight capacity is a value between the weight capacities of the exemplified activated carbon made from the same binder (i.e., SA-1500 of Example 6 and coconut shell activated carbon of Example 5). This may be due to the type of binder, the concentration of binder and the density of activated carbon, thus requiring a larger monolith mass per GGE for reversible storage.

Example 2: Alkaline activated carbon bonded with PTFE. The alkali activated wood-based carbon was mixed with a water-diluted 60 wt% aqueous PTFE dispersion to form a 50 wt% total moisture blend, which was then mixed and sheared in a Simpson pilot muller. The amount of binder was 5 wt% PTFE relative to total solids. The mulled blend was dried overnight at 110 DEG C and then compression molded to a pressure of 200 psig in a 0.7 " ID mold at 70 &lt; 0 &gt; F. This example showed the highest volumetric performance of the comparative example (lowest volume per GGE) Unlike CMC or UHMWPE binders, which require more binder to maintain integrity, 5 wt% was observed to be sufficient to form the part.

Example 3: The alkali activated carbon bonded with Kyblock ^® FG-81. Mixing the alkali activated carbon in Kyblock ^® FG-81 and Oster blender for 3 minutes to give a total solids compared to 10 wt% binder mixture. The smaller amount of this binder in the formulation seriously damaged the integrity of the part (data not shown). The mixed powder was placed in a 3 " ID preheated mold set at 230 DEG C. The mixture was held for 5 minutes and then pressurized to 7000 psig and maintained at a constant pressure for 10 minutes When the mold temperature was < As shown in Table 2, with Kyblock &lt; ( ^R) &gt; The performance of the alkaline activated carbon monolith was comparable to that of the PTFE binder and had a lower volume capacity, better than the aqueous methyl cellulose binder.

Example 4: Activated carbon derived from coconut shell bonded with UHMWPE. Activated carbon derived from coconut shells is used for many purposes and is the most commercially used activated carbon in the world. The coconut carbon used in the examples was purchased commercially from Calgon Corporation. Example 4 was prepared by mixing coconut carbon and UHMWPE (GUR ^® from Celanese Corporation) in an Oster blender for 1 minute to obtain a blend with 15 wt% binder. Low binder concentrations were not sufficient to form structural components (data not shown). The parts were prepared by adding a blend to a 1.5 inch ID mold preheated to a temperature reading of 232 DEG C, holding it for 30 minutes, and then pressurizing to 15,000 psig for 1 minute. The performance values of the parts were substantially less than those of the embodiments of the present disclosure. This is due to the binder effect on the activated carbon which has a small amount of pore volume in the desired range and significantly degrades the desired pore volume.

Example 5 Activated Carbon from Coconut Shell Combined with CMC. Activated carbon derived from a coconut shell was prepared as a monolithic component by the method outlined in Example 1. CMC Bonded Monolith Example 5 had better volume performance than Example 4 (i.e., coconut shell activated carbon bonded with UHMWPE). However, two coconut shell monoliths (i.e., coupled with CMC or UHMWPE) had similar weight performance. Coconut carbon is known as a relatively dense carbon, which is reflected in the broad inferior weight performance (high lb / GGE) of Examples 4 and 5.

Example 6: Nuchar ^® SA-1500 in combination with CMC. Nuchar ^® SA-1500 active carbon is much greater than has a significant amount of void volume in the larger micropores size, as described above, a 9-12Å, the focus of the conventional adsorbent used for gas adsorption (focal poin); Characterized by having a significant mesopore volume at 20-50 ANGSTROM. Monoliths include Nuchar ^® SA-1500 carbon as well as 2 wt% polyester 6 denier ¼ inch length non-bonded fibers (eg, 88 wt% carbon, 10 wt% CMC, 2 wt% fiber Innovation Technology, Inc. use of 4DG fiber ^®) was formed, as schematically described in the first embodiment. The polyester fibers were an added level of complexity to the process to improve the wicking of the internal moisture from the monolith through the drying and curing stages and thus to improve the physical integrity of the resulting monolith article. Example 6 was carried out considerably better than the coconut carbon embodiment in terms of reversible natural gas storage capacity, but its performance was poor compared to the examples of alkaline activated carbon, or to the examples containing Nuchar ^® and the non-aqueous binders described herein did.

Example 7: The combination as UHMWPE Nuchar ^® SA-1500 active carbon. It was mixed as described for Nuchar ^® SA-1500 and UHMWPE (GUR by the Celanese Corporation) in Example 4 in schematic form a monolith. UHMWPE significantly reduced the pore volume of the desired range, which is directly related to the worse weight and volume performance observed.

Example 8: Nuchar ^® SA-1500 activated carbon bonded with PTFE. Ratio were mixed in a 1 Nuchar ^® SA-1500 dae polytetrafluoroethylene (i. E., 5 wt% PTFE) as: Nuchar ^® SA-1500 and 60 wt% of ethylene dispersion 19 as polytetrafluoroethylene. The material was blended with the addition of similar water as in Example 2 and then dried in a tray oven (set at 110 DEG C) to evaporate the water. The dried material was placed in a 3 inch ID compression mold preheated to 210 &lt; 0 &gt; C and held for 5 minutes, then pressurized to 7,000 psi and maintained at constant pressure for 10 minutes. The use of heat improves the compression of the carbon and the binder due to the low closure of the pore volume of the desired area, which exhibits superior volume performance compared to CMC and UHMWPE. Further, if the amount of binder is small, more adsorbent can be used in the monolith. It is mentioned that the natural gas adsorption performance test for Example 8 was carried out in a 1 L Parr stainless steel reactor. The order of steps previously outlined to determine natural gas / methane adsorption performance remained the same except that an aluminum sleeve was inserted to better match the diameter of the monolith in the pressure vessel. The advantage of Parr is that the larger internal volume is closer to the internal volume of the actual fuel tank and the larger sample size reduces the size of the PV = znRT correction for natural gas in the void spade outside the monolith outer dimensions .

Monolith size dimensions and volume consistency

Tables 3, 7, and 8 compare the consistency of dimensions and volumes of cylindrical monoliths made with alternative binder formulations. As described below, minor dimensional changes or volume changes at the stage of producing the natural gas storage monolith, and little variation in such changes, are critical to maximizing the storage performance of the fuel tank.

The percent diameter change, dD, is calculated by multiplying the diameter of the initially formed monolith by the diameter of the initially formed diameter (specifically, the inner diameter of the mold or extrusion die) and after extrusion or removal from the mold and after any subsequent drying or heat treatment, It is the percentage difference of the measured diameter of the final monolith. Percent volumetric change, dV, is the relative change of the monolith volume from its initial molding, to any final drying and post-heat treatment thereof, and is induced by the cubic effect of the measured dD values. Thus, the dV value in Table 3 was calculated as 100 [(1 + dD / 100) ³ -1]. The volume change range, VCR, is the difference between the maximum and minimum dV values for each binder type in Table 3 (e.g., the VCR for the CMC binder embodiment is -15.0% and -20.6% 5.6%), a measure of the volume variability for the monolith formed with a particular binder.

Table 3. Dimensional and volume consistency comparisons of monoliths made with alternative binders

Example type carbon bookbinder bookbinder
density,
wt% diameter
change,
(dD),% volume
change,
(dD),% Volume change range,% 9 A typical implementation Nuchar ^® SA-1500 PTFE 5 1.1 3.5 2.2 10 A typical implementation Nuchar ^® SA-1500 PTFE 5 0.5 1.6 11 A typical implementation Nuchar ^® SA-1500 PTFE 5 0.4 1.3 12 A typical implementation Wood-based phosphoric activated P KYBLOCK ^® 10 0.7 2.2 1.8 13 A typical implementation Wood-based phosphate activation A KYBLOCK ^® 10 0.4 1.3 2 A typical implementation Activation of wood-based KOH KYBLOCK ^® 10 0.4 1.3 14 A typical implementation PICA PW-2 KYBLOCK ^® 10 0.1 0.4 15 Comparative Example Wood-based phosphoric activated B CMC 12.5 -5.3 -15.0 5.6 16 Comparative Example Wood-based phosphate activation C CMC 12.5 -5.4 -15.4 17 Comparative Example Wood-based phosphate activation D CMC 12.5 -5.9 -16.8 18 Comparative Example Wood-based phosphate activation E CMC 12.5 -6.0 -16.9 19 Comparative Example Wood-based phosphate activation F CMC 12.5 -6.4 -18.1 20 Comparative Example Wood-based phosphoric activated G CMC 12.5 -6.6 -18.5 21 Comparative Example Wood-based phosphoric activated H CMC 12.5 -6.7 -18.9 22 Comparative Example Wood-based phosphate activation I CMC 12.5 -6.8 -19.1 23 Comparative Example Wood-based phosphate activation J CMC 12.5 -7.4 -20.6

Monolith embodiment 9-11 of the present disclosure: combined with PTFE Nuchar ^® SA-1500. A cylindrical monolith of PTFE- bonded Nuchar ^® SA-1500 using the same 3.00 "diameter mold for the same binder, the same 5 wt% binder content and molding, was produced in the same manner as in Example 8.

Monoliths of this disclosure Examples 12-14: KYBLOCK ^® bonded-monolith. The cylindrical monolith of KYBLOCK ^® -bonded activated carbon was prepared in the same manner as in Example 3, using the same binder, the same 10 wt% binder content, and a 3.00 "inner diameter mold for molding. The phosphoric acid wood- Were used in the preparation of Example 12. The other phosphoric acid-activated A and KOH-activated wood-based carbon used in each of Examples 13 and 14 were prepared in the laboratory. PICA PW-2 is a thermally activated commercial Grade, coconut-based carbon.

COMPARATIVE EXAMPLES 15-23: Wood-based phosphoric acid-activated carbon combined with CMC. Cylindrical monoliths of CMC-bonded activated carbon were prepared using 7HF-grade Aqualon ( ^R) CMC as binder and 4.00 " inner diameter mold for molding. Phosphoric acid-activated wood- The monolithic formulation contained 85.5 wt% activated carbon, 12.5 wt% CMC, and 2 wt% polyester 6 denier x ¼ inch fibers (4DG ^® from Fiber Innovation Technology, Inc.) . The process involves adding the dry ingredients to a pilot Simpson Mueller mixer and mixing for 5 minutes and then adding water to make the total liquid to solid concentration 1: 1 and then mixing for an additional 35 minutes The non-bonded polyester fiber component improved monolith integrity through process steps.

As it is shown in Fig. 7 and Table 3, PTFE and KYBLOCK ^® present disclosure with details binder embodiment, as compared to Comparative Example coupled CMC-, with significantly less variability in the change, the dimensions thereof, the initially formed I experienced a much smaller diameter change, dD, compared to the diameter. As shown in Figure 8, the resulting volume and volume change ranges were much lower for the embodiments of this disclosure.

Since the maximum charge of the adsorbent maximizes the storage capacity of the tank and the charge of the adsorbent from the tank to the tank during manufacture is more consistently provided, a smaller value for the range of volume change is obtained, particularly for the adsorbent monolith produced for the ANG fuel tank desirable. That is, for a tank configured to accommodate monoliths below a set target dimension, the low variability of the monolith dimensions allows the monolith to be consistently formed with dimensions closer to the tank design goals, and thus allows the tank to have a larger, more consistent adsorbent Thereby enabling a larger and more consistent fuel storage capacity. Further, when using a monolith that is closer to the internal dimensions of the fuel tank container interior dimensions, there is less chance of movement and degradation of the monolithic filler in use, which is particularly desirable for passenger cars; otherwise, over time from the cracked monolith Thus, for example, there is noise and rattle. Thus, in addition to having a substantially coherent retention of useful adsorptive porosity, as well as accepting a greatly simplified process, the use of a binder based on mechanical adhesion, as described herein, Larger and more reliable adsorbent charging is possible.

A further embodiment of a monolith having an exemplary pore volume and a recoverable NG storage. Tables 4 and 9 show additional embodiments of the monoliths of this disclosure having exemplary pore volumes based on monolith volumes, and recoverable or reversible storage capacities.

The reversible NG capacity, g / LM, relative to the volumetric monolith criteria is multiplied by 10 to the reversible NG capacity (g / 100g-M) to convert from " per 100g-M " (kg / L) to calculate g / L.

Table 4. Exemplary pore volume of an exemplary monolith of this disclosure based on monolith volume and recoverable or reversible storage capacity

Example carbon bookbinder Monolith density,
kg / L air gap
volume
9-27A in size,
cc / gM Pore volume
9-27A in size,
cc / LM Reversible NG capacity,
g / 100g-M Reversible NG capacity,
g per LM Volume capacity, L-M / GGE 2 Wood-based KOH
Activation 5 wt% PTFE 0.409 0.679 278 23.5 107.3 24.8 3 Wood-based KOH
Activation The heated 10 wt% KYBLOCK
0.451 0.614 277 22.6 109.4 24.3 12 Wood-based phosphoric activated P The heated 10 wt% KYBLOCK 0.475 0.422 200 16.9 85.9 31.4 13 Wood-based phosphate activation A The heated 10 wt% KYBLOCK 0.558 0.370 206 15.9 87.0 31.7 24 Wood-based phosphate activation K 5 wt% PTFE 0.458 0.604 277 19.2 94.1 28.0 25 Wood-based phosphate activation L 5 wt% PTFE 0.396 0.654 259 19.8 89.9 29.6 26 Wood-based phosphate activation M 5 wt% PTFE 0.409 0.629 257 19.8 91.5 29.1 27 Wood-based phosphate activation N 5 wt% PTFE 0.397 0.643 255 20.3 92.8 29.0 28 Wood-based phosphate activation O 5 wt% PTFE 0.416 0.597 248 19.1 89.5 29.8 8 Wood-based phosphate activation A heated 5 wt% PTFE 0.479 0.489 222 19.5 93.4 27.5

Monoliths of this disclosure Examples 24-28: Wood-based phosphoric acid-activated carbon bonded with PTFE. Examples 24-28 were prepared similarly to Example 2. The phosphoric acid-activated wood-based carbons K to O used to make the monolith embodiment were prepared with different pore volume and pore size distributions. In contrast to the monolith formation of these examples, Example 8 used heating as part of the compression step.

Figure 9 shows that there is an increase in reversible storage performance for natural gas with increased pore volume in pores with size / diameter 9-27 A, relative to the volume reference for these replaceable combined adsorbents in Table 4. [ Examples 2, 3 and 8 of the monoliths of this disclosure appear to have a higher performance improvement than the trends of Examples 24-28 by compression under heat or special KOH activation methods used. Regardless of the trend towards improved capacity for some embodiments exceeding the pore volume of 9-27 A measured for Examples 24-28, a monolith article having an exceptional NG pore volume of 9-27 ANGSTROM Monolith excess and about 80 g / L monolith (less than about 32 LM / GGE) reversible natural gas capacity by the method described.

Additional non-aqueous binder embodiments. Substitutable polymers other than those used in the above examples can be successfully combined with carbon in a simple manner by blending the components by shearing, drying the blend and final hot pressing of the dry blend to produce a well-formed cylindrical monolith . Activated carbon was a commercial-grade Nuchar ™ SA-1500. A typical procedure is to mix about 10 wt% of polymer with total solids based on water to make the total mixture moisture content in the mortar and pestle to 50 wt%, then dry the blend at 110 &lt; 0 &gt; C overnight, The resulting blend was compressed in a piston die mold heated to a temperature 10 [deg.] C above the softening point of the polymer.

Polyphenylene sulfide (PPS) . Celanese Fortron ^® 0205B4- rates by testing the polyphenylene sulfide powder (water content 8 wt%) were successfully formed into a cylindrical monolith. The procedure was to add 32.87 g of activated carbon to the mortar and then add a pipet aliquot of 2.67 g of FEP diluted / dispersed in 17.8 g of water. The mixture was blended for 2 minutes with a mortar and then dried. 1 " inner piston die mold was heated to 250 DEG C. An aliquot of 3.05 grams of dry material was added to the mold, the mold was pressurized to 2500 psig and held for 5 minutes at 250 DEG C. The mold was heated to about 50 Deg.] C. The molded monolithic parts were slowly depressurized and carefully vented.

Polyimide. A Michelman HP1632-grade polyimide dispersion (14.9 wt% solids) was tested and successfully formed into a cylindrical monolith. The procedure was to add 16.34 g of activated carbon to the mortar followed by the addition of a pipette aliquot of 8.95 g of polyimide diluted with 1.4 g of water. The mixture was blended in a mortar for 90 seconds and then dried. 1 " inner piston die mold was heated to 240 DEG C. An aliquot of 5.16 grams of dry matter was added to the mold and the mold was pressurized to 2500 psig after 2 minutes of rest and maintained at 250 DEG C for 5.75 minutes. / Min to 50 DEG C. The molded monolithic parts were slowly depressurized and carefully vented.

Polyamide (nylon 66). A Michelman PA845H-grade polyamide dispersion (29.3 wt% solids) was tested and successfully formed into a cylindrical monolith. The procedure was to add 16.34 g of activated carbon to the mortar and then add a pipette aliquot of 4.56 g of polyamide diluted with 5.83 g of water. The mixture was blended in a mortar for 90 seconds and then dried. 1 " inner piston die mold was heated to 190 DEG C. An aliquot of 4.62 grams of dry material was added to the mold and the mold was pressurized to 2500 psig after 2 minutes of hibernation and held for 5 minutes at 250 DEG C. The mold was heated to about 2.5 DEG C / The Michelman PA874-grade dispersion (18.3 wt% solids), available as an alternative polyamide, is a similarly good monolithic dispersion, In this example, the same amount of activated carbon was mixed with 7.28 g of the dispersion diluted to 3.07 g of water. The amount of dry blend to be compressed was 3.39 g. All other conditions were the same.

Perfluoroalkoxyalkane. The Chemours PFAD 335D-grade perfluoroalkoxyalkane (PFA) dispersion (60.75 wt% solids) was successfully tested and formed into a cylindrical monolith. The procedure was to add 32.7 g of activated carbon to the mortar followed by the addition of a pipet aliquot of 4.39 g of PFA diluted with 16.3 g of water. The mixture was blended in a mortar for 120 seconds and then dried. 1 " diameter piston die mold was heated to 190 DEG C. An aliquot of 3.23 grams of dry material was added to the mold and the mold was pressurized to 2500 psig after 2 minutes of rest and held for 5 minutes at 190 DEG C. The mold was cooled to about 2.5 DEG C / Min to 50 DEG C. The molded monolithic parts were slowly depressurized and carefully vented.

Fluorinated Ethylene Propylene. A Chemours FEPD 121-grade fluorinated ethylene propylene dispersion (8 wt% moisture) was tested and successfully formed into a cylindrical monolith. The procedure was to add 32.69 g of activated carbon to the mortar followed by the addition of a pipette aliquot of 4.62 g of FEP diluted / dispersed in 16.9 g of water. The mixture was blended for 2 minutes with a mortar and then dried. 1 " inner piston die mold was heated to 190 DEG C. An aliquot of 3.40 grams of dry material was added to the mold, the mold was paused for 2 minutes and then pressurized to 2500 psig and held at 190 DEG C for 5 minutes. Min to 50 DEG C. The molded monolithic parts were slowly depressurized and carefully vented.

The lightweight monolith embodiment of the present disclosure

Quot; hard &quot; carbon-bonded monolith blocks with relatively low surface area (e. G., &Lt; 1400 m ² / g as measured by N ₂ BET surface area) WO2017 / 031260), which is satisfactory for filtration applications in which these blocks are typically used. In contrast, soft carbons with a 1400+ m ² / g area inhibited the economical production of monoliths, but found that these materials have excellent natural gas storage capacity.

It has been found that monolith blocks for the storage of natural gas can be readily prepared by the methods of this disclosure and non-aqueous binder systems of this disclosure using only soft carbon for monolith formulation. An additional advantage of soft carbon is that it significantly reduces the monolithic fill weight for the fuel tank. Figure 5 shows the superior weight of the soft carbon formed by this disclosure, in terms of the equivalent GGE fuel capacity of the ANG fuel tank and the volume of the ANG tank. Using the expectation that a 30% reduction in vehicle weight would result in a 1% improvement in fuel economy, the use of high surface area " soft " carbon to form low density (low mass per unit volume) monoliths, It is clear that there is a significant increase in the vehicle range, exceeding the energy value of the stored fuel from 1.8% to 3.9%. Thus, by densely charging the particle adsorbent powder into the monolith, it is valuable for the natural gas adsorption capacity and has added value to the vehicle range exceeding the recoverable fuel gas in the low monolith mass obtained thereby.

Table 5. Vehicle weight reduction by low density, light carbon-based monoliths for ANG fuel tanks and improved fuel economy within the group of embodiments of this disclosure

Example 14 3 2 24 27 8 carbon Coconut thermal activation Wood-based KOH-activation
Wood-based acid-activated
Carbon "classification" "reshuffle" "Soft" "Soft" "Soft" "Soft" "Soft" bookbinder 10% KYBLOCK 10% KYBLOCK 5% PTFE 5% PTFE 5% PTFE 5% PTFE Monolith density, kg / L 0.718 0.451 0.409 0.458 0.397 0.479 Monolith BET surface area, m ² / g 908 2183 2364 1933 2136 1713 Monolith BET surface area, m 2 / cc - Monolith 652 985 967 885 848 821 Reversible NG capacity,
g / 100g 11.0 23.4 25.3 20.0 22.3 19.5 Reversible NG capacity,
G-L per monolith 79.0 105.5 103.5 91.6 88.5 93.4 Volume capacity, L-M / GGE 32.5 24.3 24.8 28.0 29.0 27.5 Weight capacity, lb / GGE 51.5 24.2 22.4 28.3 25.4 29.0 For 4GGE tanks,
Monolith Wt, lb 206 97 89 113 102 116 Difference in "hard" carbon to monolith weight vs. 4 GGE, lb --- -109 -116 -93 -104 -90 Fuel economy improvement vs. "hard" carbon for 4GGE --- -3.6% -3.9% -3.1% -3.5% -3.0% Monolith weight for 100 L tank filling, lb 159 100 90 101 88 106 Difference in "hard" carbon to monolith weight vs. 100 L, lb --- -59 -68 -57 -71 -53 "Hard" carbon for 100L fuel economy improvement --- -2.0% -2.3% -1.9% -2.4% -1.8%

Persistence of reversible natural gas capacity after multiple refueling. An often overlooked factor for the natural gas storage performance of ANG sorbents is the persistence of initial cycle performance after a number of refueling cycles, i.e. the loss of reversible capacity due to repeated pressurization and depressurization cycles. Surprisingly, the loss is related to the first cycle retention performance of the adsorbent article or monolith, and is related to the content of small micropores of 9 A in size, especially in articles quantified with < 9 angstroms < Respectively. Thus, some embodiments of the present disclosure use sorbents having a void content of these &lt; 9A size.

Table 6 is a graph showing the relationship between density, pore volume for a range of pore sizes, volume retention for a first cycle of a natural gas pressure-depressurization test, and volume retention for a repeat cycle of a pressure- And has a reversible natural gas capacity. Table 6 provides the data of Figures 10,11, and 12.

Table 6. Repeated cycles of pressurization and depressurization of the examples and comparative examples of this disclosure

Example 12 24 13 2 3 30 One 29 type A typical implementation Comparative Example carbon Wood-based phosphoric activated P Wood-based phosphate activation K Wood-based phosphate activation A Activation of wood-based KOH Wood-based phosphate activation R Activation of wood-based KOH Coconut thermal activation bookbinder KYBLOCK PTFE KYBLOCK PTFE KYBLOCK CMC CMC CMC Binder concentration, wt% 10 5 10 5 10 8 10 10 Monolith density, kg / L 0.475 0.458 0.558 0.409 0.451 0.498 0.472 0.454 Pore volume of the stated size, cc / L-M: <9 Å 47.4 64.0 103.1 122.4 129.4 57.9 118.8 171.8 9-12 Å 51.9 84.8 80.4 124.0 121.4 64.4 114.3 42.7 12-27 Å 148.4 191.9 125.9 153.7 155.3 183.7 161.5 97.2 27-50 Å 125.6 53.3 14.1 25.7 26.7 121.6 62.8 2.3 50-490Å 100.6 13.5 13.8 5.2 6.9 93.2 2.0 9.8 27-490Å 226.1 66.7 27.9 30.9 33.7 214.8 64.8 12.2 BET area, m2 / g-M 1636 1933 1309 2364 2182 1824 2045 990 BET area, m2 / cc-M 777 885 731 967 984 908 965 706 First cycle NG holding power, g / L-M 10.5 10.5 11.7 10.2 17.1 8.5 17.0 17.8 Volume capacity, L-M / GGE 31.4 28.0 30.5 24.8 24.3 27.0 20.6 30.8 The first cycle reversible NG capacity, cc / L-M 81.7 91.6 84.3 103.5 105.5 95.1 124.6 83.4 10 cycle reversible NG capacity, cc / L-M 78.4 85.6 80.9 101.4 92.9 91.1 111.9 75.6 20 cycles Reversible NG capacity, cc / L-M 85.2 72.7 Reversible capacity loss 0 → 10 cycles -4.1% -6.5% -4.0% -2.0% -12.0% -4.2% -10.2% -9.4% Reversible capacity loss 10 → 20 cycles -0.5% -3.8% Cumulative reversible capacity loss, 0 → 20 cycles -7.0% -13%

Example 29 was made with thermally activated coconut-based carbon using a combination of 88 wt% activated carbon, 10 wt% CMC binder, and 2 wt% non-binding fibers in the same manufacturing procedure as in Example 6.

Example 30 was made with phosphoric acid-activated wood-based carbon using a combination of 90 wt% activated carbon, 8 wt% CMC, and 2 wt% non-binding fibers in the same manufacturing procedure as in Example 6.

Table 7 has additional data on the density for the monolith embodiment of this disclosure, the pore volume for a range of pore sizes, and the volume retention for the first cycle of the natural gas pressure-depressurization test. Tables 6 and 7 provide data for Figures 13-16.

Table 7. Pore volume distribution data for the monolithic embodiments of this disclosure

Example 25 27 26 28 8 14 carbon Wood-based phosphate activation L Wood-based phosphate activation N Wood-based phosphate activation M Wood-based phosphate activation O Wood-based phosphate activation Q Coconut thermal activation bookbinder PTFE PTFE PTFE PTFE PTFE KYBLOCK Binder concentration, wt% 5 5 5 5 5 10 Monolith density, kg / L 0.396 0.397 0.409 0.416 0.479 0.718 Pore volume of the mentioned size, cc / L-M <9 Å 44.2 48.1 52.4 64.0 67.5 152.8 9-12 Å 67.5 68.6 69.0 77.1 57.1 42.0 12-26.5 Å 191.3 186.8 188.4 171.2 165.3 84.3 26.5-50Å 91.1 81.0 83.7 50.2 101.8 9.5 50-490Å 29.0 41.5 37.6 14.8 84.7 18.2 27-490Å 120.1 122.5 121.3 65.1 186.5 27.7 BET area, m2 / g-M 2174 2136 2119 1944 1713 908 BET area, m2 / cc-M 861 848 867 809 821 652 NG retention, g / L 4.0 4.0 4.9 5.4 11.5 15.8

10 based on the g / L-monolith reversible capacity and the percent cumulative loss compared to the first cycle reversible capacity. For both examples tested for 20 cycles, monolithic Example 24 Is superior to Comparative Example 29 in terms of the level of reversible natural gas storage capacity for a given number of cycles, particularly in terms of capacity durability (durability). That is, in contrast to the significant additional loss in the subsequent cycle according to Comparative Example 29, the relative loss of capacity for the first 10 cycles compared to the first cycle is much less in Example 24, and the additional loss There is no.

Without wishing to be bound by theory, it is believed that the loss of reversible capacity is due to the accumulation of high boiling components and contaminants commonly present in the fuel mixture, known as natural gas, which is then used as the fuel storage adsorbent And the reversible capacity performance is impaired. Further, it is believed that pores of smaller size will have greater energy or adsorptive strength, as will be readily appreciated by those skilled in the adsorbent arts. Adsorbents with pore volumes that are skewed away from excessively small pores will tend to have less of this accumulation of high boiling components and thus its reversible capacity is said to be more persistent for repetitive refueling. The test gas used in this example is similar to the general analysis of natural gas in North America, but may have a composition that is significantly higher than that of methane (see the North American Energy Standards Board natural gas specs sheet, www.naesb.org/pdf2/wgq_bps100605w2.pd). It is therefore evident that the loss of reversible capacity depends on the composition of the natural gas and therefore the more sustainable adsorbent will have a more reliable fuel storage capacity than the less sustainable adsorbent Variably less or less affected depending on the composition).

In support of this mechanism for persistence, FIG. 12 shows the correlation between the greater loss of reversible capacity in the repeat cycle and the greater retention performance of the adsorbent monolith measured from the first pressurization-decompression cycle. For example, a loss of less than 6% of the reversible capacity for the first 10 cycles is associated with a first cycle retention of less than 12 g / L-monolith. Example 24 has a sustained reversible capacity for 10-20 cycles as compared to the apparently poor persistence of Cycles 10-20 according to Example 29 having a first cycle retention of 17 g / L-monolith, with about 10 g / L-monolith has natural gas retention for its first cycle.

To obtain good continuity in reversible capacity, As embodied by embodiments having low retention in the first cycle, Figure 13 shows that less volume is desired in pores smaller than 9 angstroms in size. For example, a first cycle retention of less than 12 g / L-monolith is associated with a pore volume less than the size of 9 A less than 100 cc / L-monolith. Focusing on a 9-12 A size / diameter and a size / diameter less than 9 A, without the benefit of understanding sustainability, as shown in Table 6 and Figure 15, leads to less volume of micropore at <9 A pore size, And thus the reversible capacity is lowered because the sample having a lower volume in a pore of 9 A is smaller in pore volume of 9-12 ANGSTROM. In fact, the focus on the larger 9-27 ANGSTROM pore volume of the present disclosure for the increased reversible capacity does not provide sufficient guidance for good persistence. For example, as shown in FIG. 16, there is a similar pore volume of 200-277 cc / L 9-27A in size for an embodiment having a pore volume range of <9A, and some are substantially larger , The other is substantially less, with a pore size of < 9A, of 100 cc / L.

A pore size greater than 27 ANGSTROM or even greater than 50 ANGSTROM may be too large in a significant storage capacity due to the condensed adsorbed phase, but it is desirable that the volume for gas pressure-decompression inside the component adsorbent particles within the monolith It is still important to be able to make significant contributions to reversible capacity. As shown in Figure 14, due to the chemical and physical action of the thermal and chemical activation processes, the volume of the microvoids decreases (here represented by pores smaller than 9 angstroms), to a median pore range (Here represented by a range of 27-490 angstroms), it is common to expect an increased amount of pores of larger size. Thus, by operating within a reduced pore volume at a size of less than 9 A of some embodiments of the present disclosure, the monolith article produces a condensed phase beyond the reversible capacity that can be achieved by maximizing the volume at a pore size of 9-27 ANGSTROM An advantage of the improved reversible capacity from the internal compressed gas in the pores, which is understood to be too large to be obtained, can be obtained. 14, when the volume of microvoids smaller than 9 angstroms is less than 100 cc / L-monolith, these larger mesopore volumes of 27-490 angstroms are larger than 50 cc / L-monolith.

Overall, the need for a high reversible capacity for natural gas provided by increased pore volume in a pore of about 9-27 A pore size, the need for a persistent reversible capacity in the case of repetitive press cycles, and the advantages of compressed gas storage pores And the pore volume distribution of the adsorbent monolith product of the present disclosure is less than about 100 cc / LM in pores less than about 9 angstroms, greater than 200 cc / LM in pores of about 9-27 angstroms, about 27- About 50 cc / LM volume in a 490 A wide pore, or a combination thereof. Further, by maximizing the pore volume of both about 9-27A and about 27-490A, the mass of the adsorbent monolith is minimized for a given high density packing of the powder for the article, and thus the fuel economy advantage of lightweight fuel storage media / RTI &gt;

Specific implementations:

According to one aspect, the present disclosure provides a method of storing gas. The method comprises: contacting the gas with at least one porous gas adsorbent monolith having a working gravity capacity of? 40 lbs / GGE and / or a volume capacity of? 35 L / GGE.

In any of the aspects or embodiments described herein, the porous gas adsorbent monolith has a volume of about 100 cc / L-M at a pore size of less than about 9 angstroms; &Gt; about 200 cc / L-M volume at about 9-27 A pore size; &Gt; about 50 cc / L-M volume in pores of about 27-490 ANGSTROM; A part density of at least 0.4 g / cc; Or &lt; RTI ID = 0.0 &gt;# &lt; / RTI &gt; cc / g; Or a combination thereof.

In any aspect or embodiment described herein, the working weight capacity is? 40 lbs / GGE.

In any aspect or embodiment described herein, the volume capacity is 30 L / GGE or less.

In any aspect or embodiment described herein, the porous gas adsorbent monolith comprises a gas adsorbing material and a non-aqueous binder, as described herein.

In any aspect or embodiment described herein, the non-aqueous binder is selected from the group consisting of fluoropolymers, polyamides, polyimides, fibrillated celluloses, high-performance plastics, copolymers with fluoropolymers, A copolymer with polyimide, a copolymer with high performance plastic, or a combination thereof.

In any aspect or embodiment described herein, the fluoropolymer is at least one of poly (vinylidene difluoride), polytetrafluoroethylene, or a combination thereof.

In any aspect or embodiment described herein, the polyamide is at least one of nylon-6,6 ', nylon-6, or a combination thereof.

In any aspect or embodiment described herein, the high performance plastic is at least one of polyphenylene sulfide, polyketone, or polysulfone.

In any aspect or embodiment described herein, the non-aqueous binder is present in an amount of up to 10 wt%; The gas adsorbent material is present in an amount of at least 90 wt%; The non-aqueous binder is a dispersion of from about 50 wt% to about 70 wt% of the binder; Or a combination thereof.

In any aspect or embodiment described herein, the non-aqueous binder is present in an amount from about 2.5 wt% to about 7 wt%; The gas adsorbent material is present in an amount of at least about 93 wt%; The non-aqueous binder is a dispersion of from about 55 wt% to about 65 wt% binder; Or a combination thereof.

In any aspect or embodiment described herein, the gas adsorbing material is at least one of activated carbon, zeolite, silica, a metal organic framework, a covalent organic framework, or a combination thereof.

In any of the aspects or embodiments described herein, the activated carbon is derived from wood, peat moss, coconut shells, coal, walnut shells, synthetic polymers, and / or natural polymers.

In any aspect or embodiment described herein, the activated carbon is thermally activated, chemically activated, or a combination thereof.

According to another aspect, the present disclosure provides a porous gas adsorbent monolith. The porous gas sorbent monolith comprises a gas adsorbent material and the porous gas sorbent monolith has a working gravity capacity of? 40 lbs / GGE and / or a volume capacity of? 35 L / GGE.

In any aspect or embodiment described herein, the gas sorbent monolith further comprises a non-aqueous binder as described herein.

In any aspect or embodiment described herein, the non-aqueous binder is selected from the group consisting of fluoropolymers, polyamides, polyimides, fibrillated celluloses, high-performance plastics, copolymers with fluoropolymers, A copolymer with polyimide, a copolymer with high-performance plastics, or a combination thereof.

In any aspect or embodiment described herein, the fluoropolymer is at least one fluoropolymer selected from the group consisting of poly (vinylidene difluoride) and polytetrafluoroethylene.

In any of the aspects or embodiments described herein, the polyamide is at least one polyamide selected from the group consisting of nylon-6,6 'and nylon-6.

In any aspect or embodiment described herein, the non-aqueous binder is present in an amount up to 10 wt%.

In any aspect or embodiment described herein, the gas adsorbing material is present in an amount of at least 90 wt%.

In any aspect or embodiment described herein, the gas adsorbing material is at least one of activated carbon, zeolite, silica, a metal organic framework, a covalent organic framework, or a combination thereof.

In any of the aspects or embodiments described herein, the activated carbon is derived from wood, peat moss, coconut shells, coal, walnut shells, synthetic polymers, and / or natural polymers.

In any aspect or embodiment described herein, the activated carbon is thermally activated, chemically activated, or a combination thereof.

In any aspect or embodiment described herein, the monolith has at least one of the following: a part density of ≥ 0.4 g / cc; The working gravity capacity is ≤ 30 lbs / GGE; The volume capacity is less than 30 L / GGE; The gas adsorbent material is present in an amount of at least 93 wt%; The non-aqueous binder is present in an amount from about 2.5 wt% to about 7 wt%; The non-aqueous binder is a dispersion of from about 50 wt% to about 70 wt% of the binder; Pore volume for pores having a size in the range of about 9 A to about 27 A of &gt; = 0.5 cc / g; Or a combination thereof.

In any aspect or embodiment described herein, the part density ranges from about 0.4 g / cc to about 0.75 g / cc.

In any aspect or embodiment described herein, the part density ranges from about 0.4 g / cc to about 0.6 g / cc.

In any aspect or embodiment described herein, the working weight capacity is? 28 lbs / GGE.

According to a further aspect, the present disclosure provides a method of manufacturing a porous gas adsorbent monolith. The method comprising: mixing a gas adsorbing material and a non-aqueous binder as described herein; And compressing the mixture into a molding structure or extruding the mixture into a shape.

In any aspect or embodiment described herein, the method further comprises applying heat to the compressed mixture.

In any aspect or embodiment described herein, the monolith has at least one of the following: a non-aqueous binder includes a fluoropolymer, a polyamide, a copolymer with a fluoropolymer, a copolymer with a polyamide, Or at least one of the combinations; Or the gas adsorbing material is at least one of activated carbon, zeolite, silica, metal organic framework or a combination thereof; Or a combination thereof.

In any aspect or embodiment described herein, the monolith has at least one of the following: a part density of ≥ 0.4 g / cc; Working gravity capacity of ≤ 40 lbs / GGE; Volume capacity of ≤ 35 L / GGE; Pore volume for pores having a size in the range of about 9 A to about 27 A of > 0.5 cc / g; The gas adsorbent material is present in an amount of at least 90 wt%; The non-aqueous binder is present in an amount up to 10 wt%; Or a combination thereof.

In any aspect or embodiment described herein, the monolith has at least one of: a volume of about 100 cc / L-M at a pore size of less than about 9 angstroms; &Gt; about 200 cc / L-M volume at about 9-27 A pore size; &Gt; about 50 cc / L-M volume in pores of about 27-490 ANGSTROM; A part density in the range of about 0.4 g / cc to about 0.75 g / cc; The working weight capacity is less than 30 lbs / GGE; The volume capacity is less than 30 L / GGE; The gas adsorbent material is present in an amount of at least 93 wt%; The non-aqueous binder is present in an amount from about 2.5 wt% to about 7 wt%; The non-aqueous binder is a dispersion of from about 50 wt% to about 70 wt% of the binder; Or a combination thereof.

In any aspect or embodiment described herein, compressing the mixture comprises applying a pressure of at least 1250 psi.

In any aspect or embodiment described herein, the applied pressure is greater than 1,500 psi.

In any aspect or embodiment described herein, the forming structure or extruded shape is a cylinder, an egg-shaped prism, a cube, an elliptical prism, an egg-shaped prism, or a rectangular prism.

According to another aspect, the present disclosure provides a gas storage system. The gas storage system comprises a container; And a porous gas adsorbent monolith disposed within the monolith, wherein the monolith comprises a gas adsorbent material, wherein the porous gas adsorbent monolith has a working weight capacity of ≤ 40 lbs / GGE (eg, ≤ 28 lbs / GGE) and / or &Lt; 35 L / GGE (e.g., < 30 L / GGE).

In any aspect or embodiment described herein, the monolith further comprises a non-aqueous binder as described herein.

In any aspect or embodiment described herein, the monolith has at least one of the following: a non-aqueous binder includes a fluoropolymer, a polyamide, a copolymer with a fluoropolymer, a copolymer with a polyamide, Or at least one of the combinations; Or the gas adsorbing material is at least one of activated carbon, zeolite, silica, metal organic framework or a combination thereof; Or a combination thereof.

In any aspect or embodiment described herein, the monolith has at least one of the following: the gas adsorbing material is present in an amount of at least 90 wt%; The non-aqueous binder is present in an amount up to 10 wt%; The non-aqueous binder is a dispersion of from about 50 wt% to about 70 wt% of the binder; Or a combination thereof.

In any aspect or embodiment described herein, the monolith has at least one of the following: a part density of? 0.4 g / cc; Working gravity capacity of ≤ 40 lbs / GGE; <35 L / GGE volume capacity; Pore volume for pores having a size in the range of about 9 A to about 27 A of &gt; = 0.5 cc / g; The gas adsorbent material is present in an amount of at least 93 wt%; The non-aqueous binder is present in an amount of up to 7 wt%; The non-aqueous binder is a dispersion of from about 55 wt% to about 65 wt% of the binder; Or a combination thereof.

In any aspect or embodiment described herein, the container is configured to withstand at least 1,000 psi.

In any aspect or embodiment described herein, it is preferred that at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% Value and range) is in the range of 9-27 ANGSTROM.

In any aspect or embodiment described herein, 50%, 60%, 70%, 80%, 90%, 95% or more of the voids (including all values and ranges therebetween) are in the range of 9-27A .

In any aspect or embodiment described herein, greater than 60% of the voids are in the range of 9-27A.

In any aspect or embodiment described herein, greater than 70% of the voids are in the range of 9-27A.

In any aspect or embodiment described herein, greater than 80% of the pores are in the range of 9-27A.

In any aspect or embodiment described herein, greater than 90% of the voids are in the range of 9-27A.

In any aspect or embodiment described herein, greater than 95% of the pores are in the range of 9-27A.

In any aspect or embodiment described herein, any value between about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% And ranges are in the range of 12-27A.

In any aspect or embodiment described herein, 50%, 60%, 70%, 80%, 90%, 95% or more of the voids (including all values and ranges between) are in the range of 12-27A.

In any aspect or embodiment described herein, greater than 30% of the voids are in the range of 12-27 ANGSTROM.

In any aspect or embodiment described herein, greater than 40% of the voids are in the range of 12-27A.

In any aspect or embodiment described herein, greater than 50% of the pores are in the range of 12-27A.

In any aspect or embodiment described herein, greater than 60% of the voids are in the range of 12-27A.

In any aspect or embodiment described herein, greater than 70% of the voids are in the range of 12-27A.

In any aspect or embodiment described herein, more than 80% of the voids are in the range of about 12-27A.

In any aspect or embodiment described herein, the monolith of the present disclosure has: a volume of about 100 cc / L-M at a pore size of less than about 9 angstroms; &Gt; about 200 cc / L-M volume at about 9-27 A pore size; &Gt; about 50 cc / L-M volume in pores of about 27-490 ANGSTROM; Or a combination thereof.

While preferred embodiments of the present disclosure have been shown and described herein, it will be understood that such embodiments are provided by way of example only. Numerous variations, changes and substitutions will occur to those skilled in the art without departing from the spirit of the present disclosure. Accordingly, the appended claims are intended to cover all modifications within the spirit and scope of the present invention. Further, the system may include a plurality of devices for charging and / or discharging at least one device or system for charging and / or discharging the system.

The contents of all references, patents, pending patent applications and published patents cited throughout this application are expressly incorporated herein by reference.

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure described herein. Such equivalents are intended to be encompassed by the following claims. It is understood that the detailed embodiments and implementations described herein are given by way of example only for exemplary purposes and are not to be construed as limiting the invention in any way. Various modifications and variations in this regard will be apparent to those skilled in the art and are included within the spirit and scope of the present application and are considered within the scope of the appended claims. For example, the relative amounts of the components may be varied to optimize the desired effect, and additional components may be added and / or similar components may be substituted for the described one or more components. Additional advantageous features and functionality associated with the systems, methods and processes of the present disclosure will become apparent from the appended claims. Moreover, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure. Such equivalents are intended to be encompassed by the following claims.

Claims (41)

Contacting the gas storage system with a gas comprising at least one porous gas sorbent monolith having a working gravity capacity of ≤ 40 lbs / GGE and / or a volume capacity of ≤ 35 L / GGE. The method according to claim 1,
Said porous gas adsorbent monolith comprising:
&Lt; about 100 cc / LM volume in pores smaller than about 9 ANGSTROM size;
&Gt; about 200 cc / LM volume at about 9-27 A pore size;
&Gt; about 50 cc / LM volume at a pore size of about 27-490 ANGSTROM;
A part density of at least 0.4 g / cc; or
And combinations thereof. 3. The method according to claim 1 or 2,
Wherein the working weight capacity is? 40 lbs / GGE. 4. The method according to any one of claims 1 to 3,
Wherein the volume capacity is 30 L / GGE or less. 5. The method according to any one of claims 1 to 4,
Wherein the porous gas adsorbent monolith comprises a gas adsorbing material and a non-aqueous binder. 6. The method of claim 5,
The non-aqueous binder may be selected from the group consisting of a fluoropolymer, a polyamide, a polyimide, a fibrillated cellulose, a high-performance plastic, a copolymer with a fluoropolymer, a copolymer with a polyamide, a copolymer with a polyimide, &Lt; / RTI &gt; performance plastic, or a combination thereof. The method according to claim 6,
Wherein the fluoropolymer is at least one of poly (vinylidene difluoride), polytetrafluoroethylene, fluorinated ethylene propylene, perfluoroalkoxyalkane, or a combination thereof. The method according to claim 6,
Wherein the polyamide is at least one of nylon-6,6 ', nylon-6, nylon 6, 12, or a combination thereof. 9. The method according to any one of claims 5 to 8,
The binder is present in an amount of up to 10 wt%;
The gas adsorbing material is present in an amount of at least 90 wt%;
The non-aqueous binder is a dispersion of from about 50 wt% to about 70 wt% of the binder; or
And combinations thereof. 10. The method according to any one of claims 5 to 9,
The non-aqueous binder is present in an amount from about 2.5 wt% to about 7 wt%
The gas adsorbing material is present in an amount of at least 93 wt%;
The non-aqueous binder is a dispersion of from about 55 wt% to about 65 wt% of the binder; or
And combinations thereof. 11. The method according to any one of claims 5 to 10,
Wherein the gas adsorbing material is at least one of activated carbon, zeolite, silica, a metal organic framework, a covalent organic framework, or a combination thereof. 12. The method of claim 11,
Wherein the activated carbon is derived from wood, peat moss, coconut shells, coal, walnut shells, synthetic polymers and / or natural polymers. 13. The method according to claim 11 or 12,
Wherein the activated carbon is thermally activated, chemically activated, or a combination thereof. A porous gas sorbent monolith comprising a gas adsorbent material,
Wherein the porous gas adsorbent monolith has a working gravity capacity of < = 40 lbs / GGE and / or a volume capacity of &lt; 35 L / GGE. 15. The method of claim 14,
A porous gas sorbent monolith, further comprising a non-aqueous binder. 16. The method of claim 15,
The non-aqueous binder may be selected from the group consisting of a fluoropolymer, a polyamide, a polyimide, a fibrillated cellulose, a high-performance plastic, a copolymer with a fluoropolymer, a copolymer with a polyamide, a copolymer with a polyimide, Wherein the porous gas adsorbent monolith is at least one of a copolymer with a performance plastic or a combination thereof. 17. The method of claim 16,
Wherein the fluoropolymer is at least one fluoropolymer selected from the group consisting of poly (vinylidene difluoride), fluorinated ethylene propylene, perfluoroalkoxyalkane, and polytetrafluoroethylene. 17. The method of claim 16,
Wherein said polyamide is at least one polyamide selected from the group consisting of nylon-6,6 ', nylon-6, and nylon 6, 12. 12. A porous gas sorbent monolith, 19. The method according to any one of claims 15 to 18,
Wherein the non-aqueous binder is present in an amount of up to 10 wt%. 20. The method according to any one of claims 14 to 19,
Wherein the gas adsorbent material is present in an amount of at least 90 wt%. 21. The method according to any one of claims 14 to 20,
Wherein the gas adsorbent material is at least one of activated carbon, zeolite, silica, metal organic framework, covalent organic framework, or a combination thereof. 22. The method of claim 21,
The activated carbon is derived from wood, peat moss, coconut shell, coal, walnut shell, synthetic polymer and / or natural polymer. 23. The method of claim 21 or 22,
Wherein the activated carbon is thermally activated, chemically activated, or a combination thereof. 25. The method according to any one of claims 14 to 24,
Said monolith comprises:
&Lt; about 100 cc / LM volume in pores smaller than about 9 ANGSTROM size;
&Gt; about 200 cc / LM volume at about 9-27 A pore size;
&Gt; about 50 cc / LM volume at a pore size of about 27-490 ANGSTROM;
Part density of ≥ 0.4 g / cc;
The working weight capacity is? 30 lbs / GGE;
The volume capacity is less than 30 L / GGE;
The gas adsorbing material is present in an amount of at least 93 wt%;
The non-aqueous binder is present in an amount from about 2.5 wt% to about 7 wt%;
The non-aqueous binder is a dispersion of from about 50 wt% to about 70 wt% of the binder; or
Wherein the porous gas adsorbent monolith is at least one of a combination thereof. 25. The method of claim 24,
Wherein the part density is in the range of about 0.4 g / cc to about 0.75 g / cc. 26. The method according to any one of claims 14 to 25,
Wherein the part density is in the range of about 0.4 g / cc to about 0.6 g / cc. 27. The method according to any one of claims 14 to 26,
Wherein the working weight capacity is < 28 lbs / GGE. Mixing the gas-absorbing material and the non-aqueous binder; And
Compressing the mixture into a forming structure, or extruding the mixture into a shape. 29. The method of claim 28,
Further comprising applying heat to the compressed mixture. &Lt; Desc / Clms Page number 17 &gt; 29. The method of claim 28,
The monolith comprises:
Wherein the non-aqueous binder is selected from the group consisting of a fluoropolymer, a polyamide, a polyimide, a fibrillated cellulose, a high-performance plastic, a copolymer with a fluoropolymer, a copolymer with a polyamide, a copolymer with a polyimide, At least one of a copolymer with a performance plastic or a combination thereof;
Wherein the gas adsorbing material is at least one of activated carbon, zeolite, silica, metal organic skeleton, covalent organic skeleton, or a combination thereof; or
&Lt; / RTI &gt; wherein the porous gas adsorbent monolith has at least one of a combination thereof. 31. The method according to any one of claims 28 to 30,
Said monolith comprises:
&Lt; about 100 cc / LM volume in pores smaller than about 9 ANGSTROM size;
&Gt; about 200 cc / LM volume at about 9-27 A pore size;
&Gt; about 50 cc / LM volume at a pore size of about 27-490 ANGSTROM;
Part density of ≥ 0.4 g / cc;
Working weight capacity of ≤ 40 lbs / GGE;
<35 L / GGE volume capacity;
The gas adsorbent material is present in an amount of at least 90 wt%;
The non-aqueous binder is present in an amount of up to 10 wt%; or
Wherein the porous gas adsorbent monolith is at least one of a combination thereof. 32. The method according to any one of claims 28 to 31,
The monolith comprises:
The part density in the range of about 0.4 g / cc to about 0.75 g / cc;
The working weight capacity is less than 30 lbs / GGE;
The volume capacity is less than 30 L / GGE;
The gas adsorbent material is present in an amount of at least 93 wt%;
The non-aqueous binder is present in an amount from about 2.5 wt% to about 7 wt%;
Wherein the non-aqueous binder is a dispersion of from about 50 wt% to about 70 wt% of the binder; Or a combination thereof. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 33. The method according to any one of claims 28 to 32,
Wherein compressing the mixture comprises applying a pressure of at least 1250 psi. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 34. The method of claim 33,
Wherein the applied pressure is greater than 1500 psi. 35. The method according to any one of claims 28 to 34,
Wherein the molded structure or the extruded shape is a cylinder, an egg-shaped prism, a cube, an elliptical prism, an egg-shaped prism, or a rectangular prism. Container; And
A porous gas adsorbent monolith disposed within the monolith, the monolith comprising a gas adsorbent material,
The porous gas adsorbent monolith has a working weight capacity of ≤ 40 lbs / GGE (eg, ≤ 28 lbs / GGE) and / or a volume capacity of <35 L / GGE (eg, 30 L / GGE). 37. The method of claim 36,
Wherein the monolith further comprises a non-aqueous binder. 39. The method of claim 37,
The monolith comprises:
Wherein the non-aqueous binder is selected from the group consisting of a fluoropolymer, a polyamide, a polyimide, a fibrillated cellulose, a high-performance plastic, a copolymer with a fluoropolymer, a copolymer with a polyamide, a copolymer with a polyimide, At least one of a copolymer with a performance plastic or a combination thereof;
Wherein the gas adsorbing material is at least one of activated carbon, zeolite, silica, metal organic skeleton, covalent organic skeleton, or a combination thereof; or
And combinations thereof. 39. The method according to any one of claims 36 to 38,
The monolith comprises:
The gas adsorbent material is present in an amount of at least 90 wt%;
The non-aqueous binder is present in an amount of up to 10 wt%;
Wherein the non-aqueous binder is a dispersion of from about 50 wt% to about 70 wt% of the binder; Or a combination thereof. 40. The method according to any one of claims 36 to 39,
The monolith comprises:
&Lt; about 100 cc / LM volume in pores smaller than about 9 ANGSTROM size;
&Gt; about 200 cc / LM volume at about 9-27 A pore size;
&Gt; about 50 cc / LM volume at a pore size of about 27-490 ANGSTROM;
Part density of ≥ 0.4 g / cc;
Working gravity capacity of ≤ 40 lbs / GGE;
<35 L / GGE volume capacity;
The gas adsorbent material is present in an amount of at least 93 wt%;
The non-aqueous binder is present in an amount of up to 7 wt%;
Wherein the non-aqueous binder is a dispersion of from about 55 wt% to about 65 wt% of the binder; Or a combination thereof. 41. The method according to any one of claims 36 to 40,
Wherein the container is configured to withstand at least 1,000 psi.

Images